PROCESS FOR THE MANUFACTURE OF POLYBUTYLENE TEREPHTHALATE COPOLYMERS FROM POLYETHYLENE TEREPHTHALATE, AND COMPOSITIONS AND ARTICLES THEREOF

Description

[0001] This disclosure relates to a process for the manufacture of polybutylene terephthalate from polyethylene terephthalate, and compositions and articles thereof.

[0002] Thermoplastic molding compositions based on polybutylene terephthalate (PBT) are used in various applications. Although useful to many customers, conventional PBT molding compositions generally cannot be made from recycled sources of PBT due to the lack of availability of large post-consumer or post-industrial supplies of PBT scrap materials. Polyethylene terephthalate (PET), unlike PBT, is made in much larger quantities and is more easily recovered from consumer wastes.

[0003] With increasing demand for conserving non-renewable resources and more effectively recycling underutilized scrap PET, improved and less costly processes for deriving PBT from scrap PET materials are sought, in particular if the resulting derived PBT compositions possess desirable physical properties such as tensile and impact strength, and thermal properties. It would be particularly advantageous if the process were compatible with PET blend compositions comprising other polymer components and/or impurities.

[0004] The present invention relates to a process as defined in claim 1. The present invention relates also to a composition as defined in claim 10 and to an article as defined in claim 16.

[0005] Our invention is based on the discovery that it is now possible to make commercially useful modified poly(butylene terephthalate) copolymers from post-consumer and post-industrial poly(ethylene terephthalate) sources that contain other polymers, namely polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, and polylactic acid. We have also discovered specific amounts of the polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, and polylactic acid that can be present so that modified poly(butylene terephthalate) copolymers containing such materials exhibit preferred properties and are useful for commercial purposes. We have also discovered specific amounts of the polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6 that render compositions unsuitable for commercial purposes.

[0006] More particularly, our invention is based on the discovery that polyethylene terephthalate (PET) can be converted to what is referred to herein as a modified polybutylene terephthalate (PBT), starting from PET blend compositions comprising at least one additional polymer, for example a polyvinyl chloride. The modified PBT compositions have physical properties suitable for commercial molding applications. Unlike conventional molding compositions containing virgin PBT (PBT prepared from monomers), the modified PBT used in the molded articles contains a polyethylene terephthalate residue, e.g., materials such as ethylene glycol and isophthalic acid groups (components that are not present in "virgin," monomer-based PBT). In some instances the modified PBT molding compositions exhibit improved flow and mechanical properties compared to molding compositions comprising virgin PBT. The process provides a valuable way to effectively recycle post-consumer or post-industrial streams of scrap PET for utilization in PBT molding applications. Further, the process can aid in the conservation of non-renewable resources and reduce the formation of greenhouse gases, e.g., CO₂.

[0007] As used herein the singular forms "a," "an," and "the" include plural referents. The term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill. Compounds are described using standard nomenclature. The term "and a combination thereof' is inclusive of the named component and/or other components not specifically named that have essentially the same function.

[0008] The term "random copolymer," as used in this application refers to a copolymer that includes macromolecules in which the probability of finding a given monomeric unit at any given site in the chain is independent of the nature of the adjacent units.

[0009] Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values. The endpoints of all ranges reciting the same characteristic or component are independently combinable and inclusive of the recited endpoint. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations. The term "from more than 0 to" an amount means that the named component is present in some amount more than 0, and up to and including the higher named amount.

[0010] All ASTM tests and data are from the 2003 edition of the Annual Book of ASTM Standards unless otherwise indicated.

[0011] With respect to the terms "terephthalic acid group," "isophthalic acid group," "ethylene glycol group," "butanediol group," and "diethylene glycol group" being used to indicate, for example, the weight percent (wt.%) of the group in a molecule, the term "isophthalic acid group(s)" means the group or residue of isophthalic acid having the formula (-O(CO)C₆H₄(CO)-), the term "terephthalic acid group" means the group or residue of isophthalic acid having the formula (-O(CO)C₆H₄(CO)-), the term "diethylene glycol group" means the group or residue of diethylene glycol having the formula (-O(C₂H₄)O(C₂H₄)-), the term "butanediol group" means the group or residue of butanediol having the formula (-O(C₄H₈)-), and the term "ethylene glycol group" means the group or residue of ethylene glycol having the formula (-O(C₂H₄)-).

[0012] In general, the modified PBT copolymer (which can also be referred to as PET-modified PBT, or PET-derived PBT) is made by a process wherein the PET component is depolymerized in the presence of 1,4-butanediol and at least one second polymer selected from polyvinyl chloride, a polyvinylidene chloride, a polyamide, a polylactic acid, or a combination thereof, followed by polymerization of the depolymerized PET component with 1,4-butanediol, and a catalyst.

[0013] The PET component from which the modified PBT copolymer is made can be in a variety of forms. Generally, the PET component includes recycle (scrap) PET in flake, powder/chip, film, or pellet form. Before use, the PET is generally processed to remove impurities such as paper, adhesives, polyolefin, e.g., polypropylene, polyvinyl chloride (PVC), nylon, polylactic acid (an aliphatic polyester), and other contaminants. However, the examples herein demonstrate that effective conversion of PET to modified PBT is possible when polyvinyl chloride, polyvinylidene chloride, nylon 6, nylon 6,6, and/or polylactic acid are present during the process. Also, the PET component can include PET that is not waste in flake, chip, or pellet form. As such, PET that would ordinarily be deposited in landfills can now be used productively and effectively. In one embodiment, the PET component can also include other polyesters and/or polyester copolymers derived from aromatic dicarboxylic acids. Examples of such materials include polyalkylene terephthalates such as polyethylene terephthalate, polycyclohexane terephthalate, copolyesters of terephthalate esters with comonomers containing cyclohexanedimethanol and ethylene glycol, copolyesters of terephthalic acid with comonomers containing cyclohexanedimethanol and ethylene glycol, polybutylene terephthalate, polyxylylene terephthalate, polydianol terephthalates, polytrimethylene terephthalate, polyester naphthalates, and combinations thereof.

[0014] In one embodiment, the 1,4-butanediol used in the manufacture of the modified PBT copolymer component is derived all or in part from a biomass, e.g., is a corn-derived 1,4-butanediol or a 1,4-butanediol derived from a cellulosic material. The term "biomass" means living or dead biological matter that can be directly or subsequently converted to useful chemical substances that are ordinarily derived from non-renewable hydrocarbon sources. Biomass can include cellulosic materials, grains, starches derived from grains, fatty acids, plant-based oils, among others. When this embodiment is used, the manufacture of compositions containing the modified polybutylene terephthalate can further reduce CO2 emissions that are ordinary generated when PBT is made from fossil fuel derived monomers. Also, this further reduces the amount of non-renewable hydrocarbon sources that are used in order to make the PBT.

[0015] In one specific method for the manufacture of the modified PBT copolymer, the PET component is (a) depolymerized in the presence of 1,4-butanediol, a catalyst, and at least one second polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, nylon 6, nylon 6,6, polylactic acid, and a combination thereof. The depolymerization step provides a molten mixture of oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing butylene terephthalate groups, oligomers containing butylene isophthalate groups, and covalently bonded oligomeric moieties containing at least two of the foregoing groups. Suitable conditions for effecting the depolymerization include a pressure that is at least atmospheric pressure; and a temperature ranging from 180°C to 230°C. The depolymerization mixture can optionally be agitated under an inert atmosphere. As such, our process converts poly(ethylene terephthalate) waste, e.g., the PET component to the modified poly(butylene terephthalate) copolymer by breaking down the poly(ethylene terephthalate) to its constituent monomers, or oligomers.

[0016] In a subsequent step (b), the temperature of the molten mixture is raised, and the pressure is decreased to subatmospheric pressure, to form the modified PBT copolymer, comprising polyester units selected from the following formulas (1), (2), (3), (4):



wherein D is a 1,4-butylene (-(C₄H₈)-); D' is ethylene (-(C₂H₄)-); R' is terephthalylene (-1,4-(C₆H₄)-); and R" is an isophthalylene (-1,3-(C₆H₄)-).

[0017] The 1,4-butanediol can be continuously refluxed back into the reactor during the depolymerization. In one embodiment, 1,4-butanediol is refluxed back into the reactor during the depolymerization (step(a)). In another embodiment, excess 1,4-butanediol, ethylene glycol, and tetrahydrofuran are removed during the polymerization (step(b)).

[0018] The PET component and the 1,4-butanediol component are generally combined under atmospheric pressure. It is also possible to use pressures that are higher than atmospheric pressures, for example 100 kPa to 500 kPa absolute. For instance, in one embodiment, the pressure at which the PET component and the 1,4-butanediol are subjected to is 200 kPa (2 atmospheres), or higher. With higher pressures, depolymerization can occur at temperatures higher than 230°C.

[0019] The temperature at which the PET component, the 1,4-butanediol, and the at least one second polymer are combined and reacted is sufficient to promote depolymerization of the PET component into components such as polyethylene terephthalate and polybutylene terephthalate oligomers, 1,4-butanediol, and ethylene glycol. More particularly, the PET component is depolymerized into oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing butylene terephthalate groups, oligomers containing butylene isophthalate groups, and covalently bonded oligomeric moieties containing at least two of the foregoing moieties. The temperature at which the PET component and the 1,4-butanediol component are combined is generally from 180°C to 230°C.

[0020] The 1,4-butanediol is generally used in excess amount relative to the PET component. In one embodiment, 1,4-butanediol is used in a molar excess amount ranging from 2 to 20, based on the moles of polyethylene terephthalate repeating unit.

[0021] During the initial stage of the process when the PET component and the 1,4-butanediol are combined and reacted (step (a)), the PET component depolymerizes into a molten mixture. As described above, the molten mixture contains at least polyethylene terephthalate and polybutylene terephthalate oligomers, 1,4-butanediol, and ethylene glycol. The 1,4-butanediol and ethylene glycol are generally recirculated, and tetrahydrofuran is distilled off during this step of the process. In one embodiment, the PET component can be also depolymerized with ethylene glycol or propylene glycol.

[0022] The duration of the depolymerization step is at least 30 minutes, depending on factors such as the equipment used, production needs, desired final properties, and the like. In one embodiment, the depolymerization step is carried out in at least 2 hours. In another embodiment, the depolymerization step is carried out in from 2 to 5 hours.

[0023] The process further includes the step of polymerizing the molten mixture at subatmospheric pressure and at an increased temperature of at least 230°C, more particularly 230°C to 260°C, thereby forming the modified PBT copolymer derived from the PET component (step (b)).

[0024] Generally, the molten mixture is subjected to a second pressure lower than the first pressure. In one embodiment, the first pressure is reduced to a second pressure of 13.3 kPa to 0.0067 kPa in a continuous manner. In another embodiment, the first pressure is reduced to a second pressure of 1.33 kPa to 0.0134 kPa in a continuous fashion. More particularly the second pressure is less than 0.3 kPa absolute. Advantageously, the molten mixture can be placed under subatmospheric conditions without isolation and dissolution of any material from the molten mixture. The avoidance of this step greatly enhances the utility of the process. The polymerization is conducted with agitation and under an inert atmosphere.

[0025] The temperature at which the molten mixture is placed under subatmospheric conditions is sufficiently high to promote polymerization of the polyethylene terephthalate and polybutylene terephthalate oligomers, 1,4-butanediol, and ethylene glycol. More specifically, the temperature is 230°C to 260°C.

[0026] During the step when the molten mixture is placed under subatmospheric conditions and the temperature is increased, excess 1,4-butanediol, ethylene glycol, and tetrahydrofuran (THF) can be removed from the reactor and oligomers are allowed to build in molecular weight. Agitation can be continuously provided to facilitate the removal of the low boiling components. After sufficient molecular weight is obtained, the resulting molten PBT polymer is dropped from the reactor, cooled, stranded, and chopped into pellets.

[0027] The duration of the step in which the molten mixture polymerizes from polyethylene terephthalate and polybutylene terephthalate oligomers, 1,4-butanediol, and ethylene glycol can vary, depending on factors such as the equipment used, production needs, desired final properties, and the like. In one embodiment, the polymerization is carried out for at least 60 minutes. In another embodiment, the polymerization step is carried out from 2 to 5 hours. The resulting mixture comprises modified PBT and at least one polyethylene terephthalate component residue. The modified PBT further comprises the at least one second polymer, at least one residue derived from the second polymer, or a combination thereof.

[0028] Both steps of the process can be carried out in the same reactor. In one embodiment, however, the process is carried out in at least two separate reactors, where step (a) is carried out in a first reactor and when the molten mixture has formed, the molten mixture is placed in a second reactor and step (b) is carried out. In another embodiment, the process can be carried out in more than two reactors. In another embodiment, the process can be carried out in a continuous series of reactors.

[0029] A catalyst can be used to facilitate the reaction. Exemplary catalysts include antimony compounds, tin compounds, titanium compounds, combinations thereof as well as many other metal catalysts and combinations of metal catalysts that have been disclosed in the literature. The amount of the catalyst will vary depending on the specific reaction components and conditions, and can be from 1 to 5000 ppm, or more. The catalyst component is generally added in step (a), during the initial combining of the PET component, the 1,4-butanediol, and the ionic monomer. In another embodiment, the catalyst component can be added to the molten mixture that forms after the PET component and the 1,4-butanediol are combined and reacted. The catalyst can also be added during both the depolymerization and polymerization steps.

[0030] The process for making the modified copolymer is preferably carried out under agitative conditions. The term "agitative conditions" or "agitation" refers to subjecting the PET component, the at least one second polymer, and the 1,4-butanediol to conditions that involve physical mixing of the PET component, the at least one second polymer, and 1,4-butanediol and promote the depolymerization of the PET in step (a), and/or subjecting the molten mixture to conditions that involve physically mixing the molten mixture to promote polymerization to form the modified PBT from polyethylene terephthalate oligomers, polybutylene terephthalate oligomers, 1,4-butanediol, and ethylene glycol in step (b). The physical mixing can be accomplished by methods known in the art. In one embodiment, a mixer containing rotating shaft and blades that are perpendicular to the shaft is used.

[0031] The process can include a step that reduces the amount of THF produced during the process by adding a basic compound containing an alkali metal to the reactor in the depolymerization step (a), polymerization step (b), or combination thereof, and thereby reducing formation of THF. The basic compound contains an alkali metal and can be, for example, sodium alkoxides, sodium hydroxide, sodium acetate, sodium carbonate, sodium bicarbonates, potassium alkoxides, potassium hydroxide, potassium acetate, potassium carbonate, potassium bicarbonate, lithium alkoxides, lithium hydroxide, lithium acetate, lithium carbonate, lithium bicarbonate, calcium alkoxides, calcium hydroxide, calcium acetate, calcium carbonate, calcium bicarbonates, magnesium alkoxides, magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium bicarbonates, aluminum alkoxides, aluminum hydroxide, aluminum acetate, aluminum carbonate, aluminum bicarbonates, and combinations thereof. The amount of the basic compound added to a mixture is generally at least 0.1 ppm, specifically from 0.1 to 50 ppm, more specifically from 1 to 10 ppm, each based on the parts by weight of the modified poly(1,4-butylene terephthalate) copolymer. The addition of the basic compound containing an alkali metal can reduce the amount of total THF production, as compared to when the process is carried out without the basic compound. In one embodiment, the total THF produced during the process is reduced by at least 10%, as compared to a process that does not use the basic compound. In another embodiment, the total THF produced during the process is reduced ranges from at least 10% to 50%, or more. In another embodiment, the THF is reduced from at least 10% to 50%.

[0032] A difunctional epoxy compound can optionally be added to reduce the formation of THF. The epoxy compounds may be selected from the group of difunctional epoxies. Examples of suitable difunctional epoxy compounds include 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene di-epoxide, bisphenol diglycidyl ethers such as bisphenol-A diglycidyl ether, tetrabromobisphenol-A diglycidyl ether, glycidol, diglycidyl adducts of amines and amides, diglycidyl adducts of carboxylic acids such as the diglycidyl ester of phthalic acid the diglycidyl ester of hexahydrophthalic acid, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, butadiene diepoxide, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and the like. Especially preferred is 3,4-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate. The amount of the epoxy added to the mixture is generally present in an amount of at least 0.05 wt.% (wt.%), specifically from 0.1 to 1 wt.%, more specifically from 0.2 to 0.5 wt.%, each based on the weight of the modified poly(1,4-butylene terephthalate) copolymer.

[0033] In another method for the manufacture the modified PBT copolymer, a three-step process is used. In this process, the PET component is (a) depolymerized in the presence of the at least one second polymer, ethylene glycol, propylene glycol, or a combination thereof, under conditions effective to provide a first molten mixture of oligomers containing ethylene terephthalate moieties, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing trimethylene terephthalate groups, oligomers containing trimethylene isophthalate groups, and covalently bonded oligomeric groups containing at least two of the foregoing groups. The first molten mixture further comprises the at least one second polymer, a residue derived from the second polymer, or a combination thereof. Suitable conditions for effecting the depolymerization include a pressure that is at least atmospheric pressure; a temperature ranging from 190°C to 250°C; and an inert atmosphere. The depolymerization of the PET component can be carried out for various times. In one embodiment, the depolymerization is carried out for at least 25 minutes.

[0034] In step (b) of the three-step process, 1,4-butanediol is added to the first molten mixture under conditions that are effective to form a second molten mixture containing a component selected from the group consisting of oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing trimethylene terephthalate groups, oligomers containing trimethylene isophthalate groups, oligomers containing butylene terephthalate groups, oligomers containing butylene isophthalate groups, covalently bonded oligomeric moieties containing at least two of the foregoing groups, and combinations thereof. The second molten mixture further comprises the at least one second polymer, a residue derived from the second polymer, or a combination thereof. Suitable conditions for forming the second molten mixture are in a reactor in the presence of a catalyst component at a temperature ranging from 190 °C to 240 °C.

[0035] In a subsequent step (c) of the three-step process, the temperature of the molten mixture is raised, and the pressure is decreased to subatmospheric pressure, to form the modified PBT copolymer, comprising polyester units selected from the following formulas (1), (2), (3), (4), (5), (6):





wherein D is 1,4-butylene (-(C₄H₈)-); D' is ethylene (-(C₂H₄)-); D" is 1,2-tripropylene, 1,3-tripropylene, or a combination thereof; R' is terephthalylene (-1,4-(C₆H₄)-); and R" is isophthalylene (-1,3-(C₆H₄)-).

[0036] It will be appreciated that the components in the first and second molten mixtures can vary, depending on the diol used in the depolymerization step (a) of the three-step process. When the PET component is depolymerized with ethylene glycol, the first molten mixture contains oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, covalently bonded oligomeric moieties containing at least two of the foregoing groups, ethylene glycol, and combinations thereof. When the PET component is depolymerized with propylene glycol, the first molten mixture contains oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing trimethylene terephthalate groups, oligomers containing trimethylene isophthalate groups, covalently bonded oligomeric moieties containing at least two of the foregoing groups, ethylene glycol, propylene glycol and combinations thereof. The propylene glycol can be either 1,3- or 1,2-propylene glycol, or a combination thereof.

[0037] The diol component (ethylene glycol, propylene glycol, and combinations thereof) can be present in step (a) of this three-step embodiment in a molar amount that is at least 25%, or alternatively at least 50% of the amount of ethylene glycol moieties present in the PET component.

[0038] The compounds used in the two-step or three-step process can be reused and/or collected as the process proceeds. In one embodiment, the ethylene glycol, propylene glycol, or combination thereof and the 1,4-butanediol are removed and collected in a vessel in step (b). In another embodiment, in step (b), 1,4-butanediol is refluxed back into the reactor and excess 1,4-butanediol, ethylene glycol, propylene glycol, tetrahydrofuran, or combinations thereof is removed. The duration of step (b) can also vary. Step (b) is conducted for a sufficient period of time to reduce at least 65 % of the ethylene glycol from the second molten mixture. In one embodiment, step (b) lasts at least 45 minutes. The pressure at which step (b) is carried out can vary. In one embodiment, step (b) is carried out in atmospheric conditions. In another embodiment, step (b) is carried out in subatmospheric conditions. Different combinations are possible. In one embodiment, step (b) is carried out with excess 1,4-butanediol and at a pressure from 30 kPa to 150 kPa (300 to 1500 mbar) absolute. The 1,4-butanediol used during step (b) can be added in a molar amount that is in excess, e.g., at least 1.1 times molar excess, relative to the molar amount of 1,4-butanediol moieties incorporated into the modified PBT copolymer obtained in step (c). In another embodiment, 1,4-butanediol is used in a molar excess amount from 1.1 to 5.

[0039] Step (c) of the three-step process can also be carried out with modifications, depending on the application. In one embodiment, for instance, a component selected from the group of excess 1,4-butanediol, ethylene glycol, propylene glycol, tetrahydrofuran, or a combination thereof is removed during step (c). The pressure at which step (c) is carried out can also vary. In one embodiment, step (c) is carried out at a pressure that is less than 10 mbar.

[0040] The three-step process can be carried out in the same reactor. Alternatively, the three-step process can be carried out in at least two reactors.

[0041] This three-step process can optionally include the step of adding a basic compound as described above during step (a), step (b), step (c), or a combination thereof, to thereby further reduce THF production. Alternatively, difunctional epoxy compounds can optionally be added during step (b) in the amounts indicated above. Advantageously the three-step process can reduce the amount of THF by at least 30% as compared to the amount of tetrahydrofuran produced by the two-step process that depolymerizes the PET component with 1,4-butanediol instead of ethylene glycol, propylene glycol, or a combination thereof.

[0042] A solid-state polymerization step can optionally be used in either of the foregoing processes. The solid-state polymerization generally involves subjecting the modified PBT copolymer formed from the molten mixture to an inert atmosphere or subatmospheric pressure and heating to a temperature for a sufficient period of time to build the molecular weight of the modified PBT copolymer. Generally, the temperature to which the modified PBT copolymer is heated is below the melting point of the modified PBT copolymer, e.g., from 5 to 60°C below the melting point of the modified PBT copolymer. In one embodiment, such a temperature may range from 150 to 210°C. Suitable periods of time during which the solid-state polymerization occurs may range from 2 to 20 hours, depending on the reaction components, conditions, and equipment used. The solid-state polymerization is generally carried out under tumultuous conditions sufficient to promote further polymerization of the modified PBT copolymer to a suitable molecular weight. Such tumultuous conditions may be created by subjecting the modified PBT copolymer to tumbling, the pumping of inert gas into the system to promote fluidization of polymer particle, e.g., pellets, chips, flakes, powder, and the like. The solid-state polymerization can be carried out at atmospheric pressure and/or under reduced pressure, e.g. from 101 kPa to 0.1 kPa (1 atmosphere to 1 mbar).

[0043] The modified PBT copolymer formed by the above described methods comprises polyester units having at least one residue that is derived from a PET component, which comprises at least ethylene glycol and diethylene glycol residues. The other residue derived from the PET component can be selected from the group consisting of ethylene glycol residues, diethylene glycol residues, isophthalic acid residues, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin-containing compounds, aluminum-containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers (including cis-1,3-cyclohexane dimethanol, cis-1,4-cyclohexane dimethanol, trans-1,3-cyclohexane dimethanol, and trans-1,4-cyclohexane dimethanol), alkali salts, alkaline earth metal salts, including calcium, magnesium, sodium and potassium salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, naphthalene dicarboxylic acids, and combinations thereof.

[0044] Depending on factors such as whether polyethylene terephthalate or polyethylene terephthalate copolymers are used, the residue derived from a PET component can include various combinations. The residue includes at least mixtures of ethylene glycol and diethylene glycol. In one embodiment, the residue includes ethylene glycol, diethylene glycol and isophthalic acid. In another embodiment, at least one polyethylene terephthalate residue includes the cis isomer of 1,3-cyclohexane dimethanol, the cis isomer of 1,4-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, the trans isomer of 1,4-cyclohexane dimethanol, or combinations thereof. In another embodiment, the residue can be a mixture of ethylene glycol and diethylene glycol, in combination with isophthalic acid residues, the cis isomer of a cyclohexane dimethanol, the trans isomer of a cyclohexane dimethanol, and combinations thereof. In one embodiment, the residue derived from polyethylene terephthalate includes ethylene glycol and diethylene glycol, in combination with cobalt-containing compounds, antimony-containing compounds, isophthalic acid groups, or combinations thereof.

[0045] The amount of the ethylene glycol groups (i.e., residues), diethylene glycol groups, and the isophthalic groups in the polymeric backbone of the modified PBT copolymer can vary, and can contain, for example, isophthalic acid groups in an amount that is at least 0.1 mole %, specifically from 0 or 0.1 to 10 mole % (0 or 0.07 to 7 wt.%). The modified PBT copolymer can contain ethylene glycol in an amount that is at least 0.1 mole % and can range from 0.1 to 10 mole % (0.02 to 2 wt.%). In another embodiment, the modified PBT copolymer has an ethylene glycol content that is more than 0.85 wt.%, or alternatively 0.1 to 2 wt.%. The modified PBT copolymer can also contain diethylene glycol in an amount from 0.1 to 10 mole % (0.04 to 4 wt.%). The amount of the butanediol groups is generally about 98 mole % and can vary from 95 to 99.8 mole % in some embodiments. The amount of the terephthalic acid groups is generally about 98 mole % and can vary from 90 to 99.9 mole % in some embodiments. More particularly, the polyethylene terephthalate component residue is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, and cyclohexane dimethanol groups; and the polyethylene terephthalate component residue is in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of glycol in the modified polybutylene terephthalate copolymer. The polyethylene terephthalate component residue can further comprise isophthalic acid groups in an amount ranging from 0 to 10 mole %, based on 100 mole % of acid functionality in the modified polybutylene terephthalate random copolymer.

[0046] Unless otherwise specified, all molar amounts of the isophthalic acid groups and/or terephthalic acid groups are based on the total moles of acid functionality (diacids/diesters) in the composition. Unless otherwise specified, all molar amounts of the butanediol, ethylene glycol, and diethylene glycol groups are based on the total moles of diol in the composition. The wt.% measurements stated above are based on the way terephthalic acid groups, isophthalic acid groups, ethylene glycol groups, and diethylene glycol groups have been defined herein.

[0047] The total amount of the polyethylene terephthalate residue in the modified PBT copolymer can vary. For instance, the total amount of the residue can be from 1.8 to 2.5 wt.%, or from 0.5 to 2 wt.%, or from 1 to 4 wt.%. The ethylene glycol, diethylene glycol, and cyclohexane dimethanol groups can be individually or in combination present in an amount from 0.1 to 10 mole %, based on 100 mole % of glycol of the modified PBT copolymer. The isophthalic acid groups can be present in an amount from 0.1 to 10 mole %, based on 100 mole % of diacid/diester in the modified PBT copolymer.

[0048] When it is desirable to make a modified PBT copolymer having a melting point (Tm) that is at least 200°C, the total amount of diethylene glycol, ethylene glycol, and isophthalic acid groups can be adjusted to achieve the desired Tm. As such, in one embodiment, the total amount of the diethylene glycol, ethylene glycol, and isophthalic acid groups in the modified PBT copolymer is more than 0 and less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups in the modified PBT copolymer. In another embodiment, the total amount of the isophthalic acid groups, ethylene glycol groups, and diethylene glycol groups is from 3 to less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups in the modified PBT copolymer. In another embodiment, the total amount of the isophthalic acid groups, ethylene glycol groups, and diethylene glycol groups is from 3 to less than or equal to 10 equivalents, relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups in the modified PBT copolymer. In another embodiment, the total amount of the isophthalic acid groups, ethylene glycol groups, and diethylene glycol groups is from 10 to less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups in the modified PBT copolymer. In one embodiment, diethylene glycol, ethylene glycol, and/or isophthalic acid can be added during the process.

[0049] The total ethylene glycol groups, isophthalic acid groups, and diethylene glycol groups in the modified PBT copolymer can vary, depending on the application needs. In one embodiment, the composition can have total monomer content selected from the group consisting of ethylene glycol, isophthalic acid groups, and diethylene glycol groups in an amount from more than 0 and less than or equal to 17 equivalents relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups in the modified PBT copolymer. Advantageously, such compositions can maintain useful properties, such as heat deflection temperatures that are more than 80°C.

[0050] The total amount of inorganic residues derived from the PET component can be present in amounts from more than 0 parts per million (ppm), up to 1000 ppm, based on parts by weight of the modified PBT copolymer. Examples of such inorganic residues include of antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin containing compounds, aluminum-containing compounds, aluminum, aluminum salts, alkaline earth metal salts, alkali salts, including calcium, magnesium, sodium and potassium salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, and combinations thereof. In another embodiment, the amounts of inorganic residues can be from 250 to 1000 ppm, specifically from 500 to 1000 ppm.

[0051] As described above, the at least one second polymer can be a polyvinyl chloride, a polyvinylidene chloride, a polyamide, a polylactic acid, or a combination thereof. The second polymer can potentially also generate residues, including oligomers of polymers, during the depolymerization and/or polymerization steps.

[0052] Polyamides are a generic family of resins known as nylons, characterized by the presence of an amide group (-C(O)NH-). Nylon-6 and Nylon-6,6 are the generally used polyamides and are available from a variety of commercial sources. Other polyamides, however, such as Nylon-4,6, Nylon-12, Nylon-6,10, Nylon-6,9, Nylon-6/6T and Nylon-6,6/6T with triamine contents below 0.5 wt.%, as well as others, such as the amorphous nylons, may be useful for particular applications. A specific polyamide is Nylon-6,6. Nylon-6, for example, is a polymerization product of caprolactam. Nylon-6,6 is a condensation product of adipic acid and 1,6-diaminohexane. Likewise, Nylon-4,6 is a condensation product of adipic acid and 1,4-diaminobutane. Besides adipic acid, other useful diacids for the preparation of Nylons include azelaic acid, sebacic acid, dodecane diacid, as well as terephthalic and isophthalic acids, and the like. Other useful diamines include m-xylyene diamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl) methane, 2,2-di-(4-aminophenyl) propane, 2,2-di-(4-aminocyclohexyl) propane, among others. Copolymers of caprolactam with diacids and diamines are also useful. Polyamides that are themselves the product of a recycle process can be used. The polyamide can be present in amounts of more than 0 to less than 5.7 wt.%, more than 0 to less than 4.6 wt.%, or more than 0 to less than 1.45 wt.%, based on the total parts by weight of the polyethylene terephthalate component.

[0053] Possible residues from the polyamide include oligomers of polyamide; caprolactam, aminoacid monomers, diamine monomers, triamine monomers, and dicarboxylic acid monomers; monomeric or oligomeric terephthalimides, terephthalamides, isophthalimides, and isophthalamides formed by the condensation reaction of an amine with terephthalic or isophthalic acids or esters; monomeric or oligomeric esters formed by the reaction of ethylene glycol, 1,4-butanediol, propylene glycol, and/or cyclohexane dimethanol with the dicarboxylic acid used in the preparation of the polyamide; and combinations thereof.

[0054] Polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) include homopolymers of the general formulas (7) and (8) respectively,

wherein n is the number of repeat units in the polymers, as well as copolymers of PVC and PVDC. Potential residues derived from PVC and PVDC include ene and polyene residues formed by the dehydrochlorination of the PVC and PVDC backbone, ether residues formed by the displacement of the PVC or PVDC chloride groups by ethylene glycol, 1,4-butanediol, and cyclohexane dimethanol, and combinations thereof. The PVC or PVDC can be present in amounts of more than 0 to less than 290 ppm, or more than 0 to less than 220 ppm, based on the total parts by weight of the polyethylene terephthalate component.

[0055] Polylactic acid (PLA), an alkyl polyester, includes PLA homopolymers of the general formula (9)

and copolymers thereof. Possible PLA residues include lactide; oligomers of polylactic acid; oligomers containing lactic acid esters with terephthalate groups; oligomers containing lactic acid esters with isophthalate groups; oligomers containing ethylene lactate groups; oligomers containing diethylene lactate groups; oligomers containing propylene lactate groups; oligomers containing trimethylene lactate groups; and covalently bonded oligomeric moieties containing at least two of the foregoing groups, and combinations thereof. The polylactic acid can be present in amounts of more than 0 to less than 8 wt.% based on the total parts by weight of the polyethylene terephthalate component.

[0056] The physical properties of the modified PBT copolymer can vary, depending on factors such as the performance properties that are required, the equipment used, process parameters, the identity of the second polymer, and the like. The molecular weight of the modified PBT copolymer can be generally at least 3,000 g/mol, specifically from 10,000 to 40,000 g/mol, more specifically from 15,000 to 30,000 g/mol.

[0057] The intrinsic viscosity (IV) of the modified PBT can be at least 0.4 dL/g, specifically from 0.5 to 1.3 dL/g, more specifically from 0.4 to 1.2 dL/g. All intrinsic viscosities in this application refer to those viscosities measured in a solution of 60 wt.% phenol and 40 wt.% 1,1,2,2-tetrachloroethane at 25°C.

[0058] The melting point of the modified PBT copolymer can be at least 200°C, at least 205°C, or at least 210°C. In another embodiment, the melting point can be from 200°C to 230°C, or from 210°C to 230°C.

[0059] The flexural modulus of the modified PBT copolymer can be at least 1000 MPa, specifically from 1000 MPa to 5000 MPa, measured more specifically from 2000 to 2500 Mpa, measured in accordance with ASTM 790 or ISO 178. The tensile strength (stress at yield) of the modified PBT can be at least 30 MPa, specifically from 30 MPa to 100 MPa in accordance with ASTM D638. The tensile elongation (at yield) of the modified PBT copolymer is at least 2 % in accordance with ASTM D638.

[0060] The tensile elongation (break) of the modified PBT copolymer can be from at least 50%, more particularly 100 to 400%, measured in accordance with ASTM D638. The heat deflection temperature can be 40°C to 120°C, specifically from 40°C to 60°C at 1.82 MPa for 3.2 mm bars, measured in accordance with ASTM D648. The heat deflection temperature can be 40°C to 130°C, specifically from 50°C to 120°C at 0.455 MPa for 3.2 mm bars, measured in accordance with ASTM D648.

[0061] The notched Izod strength of the modified PBT copolymer can be at least 20 J/m, measured in accordance with ASTM D256, specifically from 20 J/m to 70 J/m, more specifically from 30 to 70 J/m at 23°C. The unnotched Izod strength of the modified PBT copolymer can be at least 500 J/m, measured in accordance with ASTM D256, specifically from 500 J/m to 3000 J/m, more specifically from 600 to 2500 J/m at 23°C, measured in accordance with ASTM D256.

[0062] Also disclosed is a composition comprising a modified PBT copolymer, comprising (a) at least one residue derived from a polyethylene terephthalate component; and (b) a member selected from the group consisting of (i) at least one polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, polyamides, polylactic acid, and combinations thereof; (ii) at least one residue derived from a polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, polyamides, polylactic acid, and combinations thereof; and (iii) combinations thereof. In one embodiment, an article comprises the composition.

[0063] The properties of the modified PBT copolymer composition vary depending on the identity of the second polymer used to produce the modified PBT polymer. For example, when the polyvinyl chloride is present in an amount of greater than 0 and less than 290 ppm based on the total parts by weight of the polyethylene terephthalate component, a molded sample of the composition can have an unnotched Izod strength of 1500 to 2500 J/m, measured in accordance with ASTM D256, and a tensile elongation at break of at least 100%, measured in accordance with ASTM D638. When the second polymer is Nylon 6 in an amount of more than 0 and less than 5.7 wt.%, based on the total weight of the polyethylene terephthalate component, a molded sample of the composition can have a tensile elongation at break that is at least 100%, measured in accordance with ASTM D638. When the second polymer is Nylon 6 in an amount of more than 0 and less than 1.45 wt.%, based on the total weight of the polyethylene terephthalate component, a molded sample of the modified polybutylene terephthalate copolymer can have a heat deflection temperature at 0.455 MPa that is at least 90°C, measured in accordance with ASTM D648. When the second polymer is Nylon 6,6 in an amount of more than 0 and less than 5.7 wt.%, based on the total weight of the polyethylene terephthalate component, a molded sample of the modified polybutylene terephthalate copolymer can have a tensile elongation at break that is at least 100%, measured in accordance with ASTM D638. When the second polymer is Nylon 6,6 in an amount of more than 0 and less than 4.6 wt.%, based on the total weight of the polyethylene terephthalate component, a molded sample of the modified polybutylene terephthalate copolymer can have a heat deflection temperature at 0.455 MPa that is at least 70°C, measured in accordance with ASTM D648.

[0064] In a more specific embodiment, a composition comprises a modified polybutylene terephthalate copolymer comprising (a) at least one residue derived from a polyethylene terephthalate component; and (b) a member selected from the group consisting of (i) at least one polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, polylactic acid, and combinations thereof; (ii) at least one residue derived from a polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, polylactic acid; and combinations thereof; and (iii) combinations thereof; wherein the modified polybutylene terephthalate copolymer is derived from a polyethylene terephthalate mixture comprising a second polymer selected from the group consisting of more than 0 to less than 290 ppm polyvinyl chloride, more than 0 to less than 5.7 wt% Nylon 6; more than 0 to less than 5.7 wt% Nylon 6,6; and more than 0 to less than 8 wt% polylactic acid, each based on the parts by weight or weight of the polyethylene terephthalate component; and the residue derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers, alkali salts, alkaline earth metal salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, napthalene dicarboxylic acids, 1,3-propanediol groups, and combinations thereof; the at least one residue derived from the polyethylene terephthalate component comprising at least mixtures of ethylene glycol and diethylene glycol. Articles can comprise the composition.

[0065] The modified PBT copolymer can be used alone, e.g., as a molding composition, or in combination with a wide variety of other thermoplastic polymers, for example other polyesters, polyolefins (e.g., polyethylenes and polypropylenes), polycarbonates (e.g., polycarbonates derived from bisphenol A), polyimides, polyetherimides, polyamides, and the like.

[0066] The modified poly(butylene terephthalate) (PBT) copolymer generally has an inherent viscosity that ranges from 0.5 to 1.4 dL/g. In one embodiment, the modified poly(butylene terephthalate) copolymer has an inherent viscosity that ranges from 0.5 to 1.2 dL/g. The melting temperature of the modified poly(butylene terephthalate) copolymer is generally at least 200 °C and can range from at least 200 °C to 235 °C. In one embodiment, the melting temperature is at least 210 °C. In one embodiment, the melting temperature of the poly(butylene terephthalate) copolymer can range from 210 °C to 235 °C.

[0067] Further, the process for making the PET-derived random, modified PBT copolymers used in the compositions can advantageously substantially reduce carbon dioxide emissions and solid waste. Since the PET-derived polyester random modified PBT copolymers made by the inventive process are made from scrap PET and not monomers, the process significantly reduces the amount of carbon dioxide emissions and solid waste. Carbon waste reduction (or crude oil savings) occurs because the carbon that constitutes the dimethyl terephthalate or terephthalic acid ordinarily used to make polyesters is not used, rather a PET component, e.g., polyester scrap, is replaced. The process to make DMT or TPA from crude oil is highly energy intensive and as a result, substantial emissions of CO2 to the atmosphere occur from burning of non-renewable energy sources. By not using DMT or TPA to make the modified PBT, carbon dioxide emissions savings are obtained. In one embodiment, the process for making modified PBT can eliminate at least 1 kg of CO₂ emissions for every kilogram of modified PBT made with the process, as compared to a process that makes virgin PBT homopolymers from monomers. In another embodiment, the process for making modified PBT can eliminate from 1 kg to 1.5 kg, or more CO₂ emissions for every kilogram of modified PBT made with the inventive process, as compared to a process that makes virgin PBT homopolymers from monomers. Additionally, there are energy savings/reduced carbon dioxide emissions when the ethylene glycol byproduct is recovered and is used instead of ordinary ethylene glycol in manufacturing.

[0068] Additionally, when the source of BDO is from biomass-derived feedstocks such as succinic acid, the carbon dioxide savings are further increased for two reasons. Biomass-derived succinic acid is made from sugars or other biomass-derived hydrocarbons that are the derived from atmospheric carbon versus fossil fuel carbon sources, thus reducing the environmental impact of the polymer derived from BDO based on succinic acid from biomass sources. Furthermore, the fermentation to yield succinic acid requires carbon dioxide as an input thus leading to further carbon dioxide reductions.

[0069] Advantageously, a molding composition containing the modified polybutylene terephthalate random copolymers can have a reduced CO₂ emissions index. The reduced CO₂ emissions index, as defined in this application, is the amount of CO₂, expressed in kg, that is saved when one (1) kg of a composition containing the modified polybutylene terephthalate random copolymers is made, as compared to the amount of CO₂, expressed in kg, that is created when the composition is made with polybutylene terephthalate that is derived from monomers. Generally, our compositions generally have a reduced CO₂ emissions index that is more than approximately 0.06 kg, and can range from 0.06 kg to 2.25.

[0070] The basis for this feature is discussed below. The difference between the amount of CO₂ that is created during ordinary processes for making virgin, monomer-derived PBT and the process for making 1 kg of the modified polybutylene terephthalate random copolymers can range from 1.3 kg to 2.5 kg, or more suitably from 1.7 kg to 2.2 kg. It should be noted that this difference is based on calculations for the entire process that starts from crude oil to the monomers to the PBT versus scrap PET to oligomers to the modified PBT. In other words, the process for making 1 kg of the modified polybutylene terephthalate random copolymers creates 1.3 to 2.5 kilograms less CO₂ as compared to the process for making 1kg of virgin PBT from crude oil. To determine the ranges of the reduced CO₂ emissions index for our compositions (which have the modified PBT random copolymers present in an amount ranging from 5 to 90 wt.%), the CO₂ reduction index can be calculated by multiplying the lower amount of the polybutylene butylene terephthalate present in the composition, in percentage terms, with 1.3 (0.05 x1.3= 0.065) and the higher amount of the polybutylene terephthalate times 2.5. (0.90x 2.5= 2.25).

[0071] These results can be derived and verified by using material and energy balance calculations (calculations that are well known in the chemical engineering art) and comparing the amount of energy used to make modified PBT random copolymers from PET and the amount of energy used to make PBT from terephthalic acid.

[0072] Advantageously, it is now possible to make modified poly(butylene terephthalate) copolymers from post-consumer and post-industrial poly(ethylene terephthalate) sources that contain other polymers, such as polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, polylactic acid. This means that it is not necessary to subject post-consumer and post-industrial poly(ethylene terephthalate) sources containing other materials to expensive processing steps. Also, it is now possible to make modified poly(butylene terephthalate) copolymers with useful amounts of polyvinyl chlorides, polyvinylidene chlorides, nylon 6, nylon 6,6, polylactic acids.

[0073] The modified PBT compositions are further described in the following illustrative examples in which all parts and percentages are by weight unless otherwise indicated.

EXAMPLES

[0074] Table 1 lists the components used in the following examples.

MATERIALS

[0075] 

Table 1

Abbreviation	Description	Supplier
PET	Recycle poly(1,4-ethylene terephthalate) pellets	N/A
PBT-1	Poly(1,4-butylene terephthalate), IV = 0.66 dl/g as measured in a 60:40 wt.% phenol/tetrachloroethane mixture at 25°C	SABIC Innovative Plastics
PBT-2	Poly(1,4-butylene terephthalate), IV = 1.0 dl/g as measured in a 60:40 wt.% phenol/tetrachloroethane mixture at 25°C	SABIC Innovative Plastics
PBT-3	Poly(1,4-butylene terephthalate), IV = 1.2 dl/g as measured in a 60:40 wt.% phenol/tetrachloroethane mixture at 25°C	SABIC Innovative Plastics
MBS	Methacrylate-butadiene-styrene emulsion copolymer impact modifier with core-shell structure	SABIC Innovative Plastics
AO	Antioxidant, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) sold as IRAGANOX™ 1010	Ciba Geigy
PVC	Polyvinyl chloride	SABIC Innovative Plastics
TPT	Titanium tetraisopropoxide	SABIC Innovative Plastics
BDO	1,4-Butanediol	SABIC Innovative Plastics
Nylon 6	NYLON 6	SABIC Innovative Plastics
Nylon 6,6	NYLON 6,6	SABIC Innovative Plastics
PLA	Polylactic acid	SABIC Innovative Plastics

TEST PROCEDURES

[0076] Intrinsic viscosity (IV) was measured in a solution of 60 wt.% phenol and 40 wt.% 1,1,2,2-tetrachloroethane at 25°C.

[0077] Melt Volume Rate (MVR) on pellets (dried for 2 hours at 120°C prior to measurement) was measured according to ISO 1133 method at 250°C and 5 kgf at dwelling time of 240 seconds and a 0.0825 inch (2.1 mm) orifice.

[0078] Capillary viscosity, which is another indicator of melt-flow was measured by ASTM D3835 or ISO D11433. Dried pellets were extruded through a capillary Rheometer and the force at varied shear rates was determined to estimate the shear viscosity.

[0079] Notched Izod impact (NII) strength was measured on 3 x ½ x 1/8 inch (76.2 x 12.7 x 3.2 mm) injection molded bars in accordance with ASTM D256. Bars were notched prior to oven aging, and samples were tested at room temperature (23°C).

[0080] Tensile elongation (TE) at break was tested on 7x1/8 in. (177.8 x 3.3 mm) injection molded bars at room temperature with a crosshead speed of 0.2 in/min (5.08 mm/min) for un-filled samples in accordance with ASTM D638.

[0081] Flexural properties (flexular modulus, flexular stress at 5% strain, flexular stress at yield) were measured in accordance with ASTM 790 method.

[0082] Biaxial impact testing, sometimes referred to as instrumented impact testing, was performed in accordance with ASTM D3763 using a 4 x 1/8 inch (101.6 x 3.2 mm) molded discs. The total energy absorbed by the sample is reported as ft-lbs or J. Testing was done at room temperature on as molded or oven aged samples.

[0083] Heat Deflection Temperature (HDT) was tested on five bars having the dimensions 5 x 0.5 x 0.125 inches (127 x 12.7 x 3.2 mm) in accordance with ASTM D648. The black specs were measured by counting the black specs present visually on the surface of a Dynatup disc.

[0084] A synopsis of all the relevant tests and test methods is given in Table 2.

Table 2

Property	Test Standard	Specimen Type	Units
Flexural Tests	ASTM D790	Bar - 127 x 12.7 x 3.2 mm	MPa
Heat Deflection Temperature (HDT)	ASTM D648	Bar - 127 x 12.7 x 3.2 mm	°C
Filled Tensile Tests	ASTM D638	ASTM Type I Tensile bar	MPa
Notched Izod Impact (NII) at 23°C	ASTM D256	Bar - 63.5 x 12.7 x 3.2 mm	J/m
Multiaxial Impact	ASTM D3763	Disk - 101.6 mm dia. x 3.2 mm thick	J
Shrinkage	GEP Method	Disk - 101.6 mm dia. x 3.2 mm thick	%
Melt Volume Rate (MVR)	ASTM D1238	Pellets	g/10 min
Energy to max load	ASTM D3763	Disk - 101.6 mm dia x 3.2 mm thick	J
Energy to failure	ASTM D3763	Disk - 101.6 mm dia x 3.2 mm thick	J
Energy Total	ASTM D3763	Disk - 101.6 mm dia x 3.2 mm thick	J

EXAMPLES 1-8. Modified PBT Copolymer Molding Compositions Containing PVC.

[0085] Examples 1 to 8 illustrate the properties of the modified PBT copolymer compositions as follows:

Example 1: modified PBT made from PET containing 115 ppm PVC

Example 2: modified PBT made from PET containing 287 ppm PVC

Example 3: modified PBT made from PET containing 575 ppm PVC

Example 4: modified PBT made from PET containing 1150 ppm PVC

[0086] Examples 1 and 3 were prepared in a helicone reactor with the capacity of 65 gallons about 200 liters) whereas Examples 2 and 4 were prepared in a helicone reactor with the capacity of 10 gallons (about 40 liters).

[0087] The raw materials used to prepare the modified PBT copolymers of Examples 1-4 are summarized in Table 3.

Table 3

Parameter	Unit	1	2	3	4
Polyester Type		Recycled PET	Recycled PET	Recycled PET	Recycled PET
BDO:PET Mole Ratio		3:1	3:1	3:1	3:1
PET	Kgs	45.4	11.4	45.4	11.4
BDO	Kgs	63.6	15.9	63.6	15.9
PVC	gms	5.2	3.25	26	13
TPT (as elemental Ti)	ppm	60	60	60	60

Examples 1 and 3. 200 Liter Pilot Plant Process (BDO:PET = 3:1)

[0088] The helicone reactor had a capacity of 200 liters and was equipped with a special design of twin opposing helical blades with 270 degree twist; constructed of 316 stainless steel with 16 g polish finish. The blade speed could be varied from 1 to 65 rpm. The agitators were connected to a Constant Torque Inverter Duty Motor, which operates at 230/460 VAC, 3 PH and 60 Hz. These agitators provided excellent surface area for the polymer melt in order to build molecular weight. The helicone was also designed with an overhead condenser to condense the vapors in the glycolysis, transesterification (if any) and polymerization stages.

[0089] 100 lbs (45.4 kg) of recycle PET pellets with 140 lbs (63.6 kg) of butanediol (BDO), (molar ratio 2.9:1) were charged to the helicone reactor. 18.8 ml (60 ppm as Ti) of titanium tetraisopropoxide (TPT) catalyst was also added to the reaction mix. PVC pellets were weighed (5.2 and 26 gms respectively for examples 1 and 3) and added to the reactor as well. The temperature of the heating oil (for the helicone) was set to 250°C. The agitator speed was set at 67 % of maximum. The butanediol was refluxed into the reactor for 2 hours. The design of the overhead condenser system did not allow a complete reflux of the butanediol. As a result, about 5 to 10 lbs (2.3 to 4.5 kg) of butanediol evolved in the initial stages could not be refluxed. The butanediol evolved after that could be completely refluxed into the reactor.

[0090] For the polymerization stage, a vacuum was applied to the helicone reactor and the reflux of butanediol to the reactor was discontinued. The speed of the agitator was set to 60 % of max and the target amps of the motor were 3.5 amps. The system pressure was brought down to 0.5 Torr (0.066 kPa) by the vacuum blower. The reaction was carried out until the polymer mass reached its third build. The reaction was stopped after 15 minutes into the third build and the polymer was cast in blobs. The products were then allowed to dry and ground into pellets.

Examples 2 and 4. 40-Liter Pilot Plant Process (BDO:PET = 3:1).

[0091] The helicone reactor had a capacity of 40 liters and was equipped with a special design of twin opposing helical blades with 270 degree twist; constructed of 316 SS with 16g polish finish. The blade speed could be varied from 1 to 65 rpm. The agitators were connected to a 7.5 HP Constant Torque Inverter Duty Motor, which operates at 230/460 VAC, 3 PH, and 60 Hz. These agitators provided excellent surface area for the polymer melt in order to build molecular weight. The helicone was also designed with an overhead condenser to condense the vapors in the glycolysis, transesterification (if any), and polymerization stages.

[0092] 25 lbs (11.4 kg) of recycle PET pellets with 35 lbs (15.9 kg) of butanediol (molar ratio 2.9:1) were charged to the helicone reactor. 4.6 ml (60 ppm as Ti) of TPT catalyst were also added to the reaction mix. PVC pellets were weighed (3.25 and 13 gms respectively for examples 2 and 4) and added to the reactor as well. The temperature of the heating oil (for the helicone) was set to 250°C. The agitator speed was set at 67 % of maximum. The butanediol was refluxed into the reactor for 2 hours. The overhead condenser system did not allow a complete reflux of the butanediol. As a result, about 5 to 10 lbs (2.3 to 4.5 kg) of butanediol evolved in the initial stages could not be refluxed. The butanediol evolved after that could be completely refluxed into the reactor.

[0093] For the polymerization stage, a vacuum was applied to the helicone reactor and the reflux of butanediol to the reactor was discontinued. The speed of the agitator was set to 60 % of max and the target amps of the motor were 3.5 amps. The system pressure was brought down to 0.066 kPa (0.5 Torr) by the vacuum blower. The reaction was carried out until the polymer mass reached its third build. The reaction was stopped after 15 minutes into the third build and the polymer was cast in blobs. The products were then allowed to dry and ground into pellets. The logic for changes in agitator speed as the molecular weight of the polymer built up is shown in Table 4.

Table 4

Stage	Build	Agitator Speed	Target Amp	Rpm
Ester Interchange	N/A	66.7 %	N/A	34
Polymerization	1st	60 %	3.5	32
	2nd	30 %	3.8	16
	3rd	18 %	4.5	9

[0094] The following tests were conducted on Examples 1-4: IV measurement, NMR analysis, and differential scanning calorimetry (DSC) analysis. The results are summarized in Table 5. Comparative Example A is a commercially available PBT (PBT-2) manufactured from monomers.

Table 5

Item	Parameter	Unit	Comparative A	1	2	3	4
	PVC ppm based on PET component	ppm	-	115	287	575	1150
DSC Data	Melting Point	°C	229.1	218.6	219.2	220.5	221.2
	Crystallization Temperature	°C	167.3	178.6	168.4	169.7	161.1
	Delta H fusion	kJ/kg	37.9	32.5	23.6	27.8	21.6
	Delta H crystallization	kJ/kg	44.9	39.7	36.7	41.2	36.3
Intrinsic Viscosity	IV	Dl/g	1.0	1.13	1.06	1.04	1.12
Composition by NMR analysis (based on total diol and diacid units)	Ethylene Glycol (EG) Repeat Unit	mol %	0.0	0.7	1.6	0.6	0.9
	Diethylene Glycol (DEG) Repeat Unit	mol %	0.0	0.2	0.4	0.2	0.3
	1,4-Butanediol (BDO) Repeat Unit	mol %	50.0	48.8	48.4	48.9	49.1
	Isophthalic Repeat Unit	Mol %	0.0	1.0	1.1	1.0	1.0
	Terephthalic Repeat Unit	Mol %	50.0	49.1	49.0	48.9	50.3
	Total Comonomers	Mol%	0.0	1.9	3.1	1.8	2.2
	Total Comonomer Equivalents	**	0.0	2.8	6.2	3.6	4.4

** Residual equivalents relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups

[0095] It is evident from the above examples that modified PBT copolymer with a comparable molecular weight to PBT made from monomers can be obtained by the processes describe herein.

[0096] The physical and mechanical properties of each of Examples 1-4 were also measured, and are summarized in Table 6.

Table 6

Property (Units)	Comparative A	1	2	3	4
PVC ppm based on PET component	-	115	287	575	1150
Modulus of Elasticity (MPa)	2600	2650	2830	2760	2450
Stress at Yield (Mpa)	53.9	54.4	48.98	49.9	48.3
Stress at Break (MPa)	31.5	38.7	48.1	49.6	5.18
Tensile Elongation at Yield (%)	3.4	3.2	2.8	2.8	2.6
Tensile Elongation at Break (%)	390.5	331.2	2.6	3.1	2.6
HDT at 0.455 MPa (°C)	111	86.65	111.6	119.2	54.3
HDT at 1.82 MPa (°C)	46.9	43.4	47.3	48.6	44.9
Notched Izod (J/m)	55.8	59.2	54.4	53.9	54.4
Unnotched Izod (J/m)	1979	2090.98	623.55	720.36	947
Flexural Modulus (MPa)	2350	2380	2440	2460	2410
Flexural Stress at 5% Strain (MPa)	78.6	75.7	82.4	81.8	78.6
Flexural Stress at Yield (MPa)	79.6	75.8	82.9	82.2	78.6
Energy to max load (J)	28.6	2.52	2.86	1.64	2.42
Energy to failure (J)	53.7	2.86	3.2	2.1	2.98
Energy Total (J)	54.3	3.72	3.6	3.3	3.02
Max Load (kN)	3.961	1.078	1.132	0.799	0.788
Deflection at max load (mm)	14	4.46	4.68	4.44	6.1
Mold Shrink Parallel (%)	1.74	1.17	2.12	1.93	1.55
Mold Shrink Perpendicular (%)	1.83	1.13	2.09	1.92	1.48
MVR (cc/10min)	17.8	28.9	29.5	23.6	20.9

[0097] The above examples demonstrate that the unnotched Izod impact strength and the elongation at break of the modified PBT copolymer samples drop substantially when the PVC concentration in the PET component is above 287 ppm (Examples 3 and 4).

EXAMPLES 5 to 8. Molding Compositions made from modified PBT containing Nylon 6.

[0098] Several molding compositions were made from modified PBT resins containing different levels of Nylon 6:

Example 5: modified PBT made from PET containing 1.15 wt.% Nylon 6

Example 6: modified PBT made from PET containing 1.44 wt.% Nylon 6

Example 7: modified PBT made from PET containing 2.9 wt.% Nylon 6

Example 8: modified PBT made from PET containing 5.7 wt.% Nylon 6

[0099] Examples 5 to 8 (modified PBT) were prepared in a helicone reactor with the capacity of 65 gallons (about 200 liters). Raw material amounts are listed in Table 7.

Table 7

Parameter	Unit	5	6	7	8
Polyester Type		Recycled PET	Recycled PET	Recycled PET	Recycled PET
BDO:PET Mole Ratio		3:1	3:1	3:1	3:1
PET Weight	Kgs	45.4	45.4	45.4	45.4
BDO Weight	Kgs	63.6	15.9	63.6	15.9
Nylon 6 Weight	gms	520	650	1300	2600
TPT as Ti element	ppm	60	60	60	60

[0100] Similar testing protocols were followed for measurement of properties as described above. DSC, IV, and composition data by NMR of the Examples 5-8 and Comparative Example A (PBT-2, prepared from its monomers) are shown in Table 8.

Table 8

Item	Parameter	Unit	Comp. A	5	6	7	8
DSC Data	Melting Point	°C	229.1	215.8	213.1	214.6	209.7
	Crystallization Temp	°C	167.3	174.2	173	173	167.9
	Delta H fusion	°C	37.9	32.1	32.6	31.8	33
	Delta H crystallization	kJ/kg	44.9	41.3	41.8	40.5	42.4
IV		Dl/g	1.0	1.06	1	0.95	0.88
Composition by NMR analysis (based on total diol and diacid units)	EG Repeat Unit	Mol %	0.0	1.4	1.9	1.4	0.7
	DEG Repeat Unit	Mol %	0.0	0.3	0.3	0.3	0.2
	BDO Repeat Unit	Mol %	50.0	48.3	47.5	47.5	46.7
	Isophthalic Repeat Unit	Mol %	0.0	1.1	1.2	1.1	1
	Terephthalic Repeat Unit	Mol %	50.0	49.1	49.0	48.9	50.3
	Total Comonomers	Mol%	0.0	2.8	3.4	2.8	1.9
	Total Comonomer Equiv.	**	0.0	5.6	6.8	5.6	3.8
	Nylon 6	Wt.%		0.9	1.1	2.1	4.4

** Residual Equivalents relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups.

[0101] It is evident from the above examples that one could make modified PBT with a comparable molecular weight to PBT prepared from monomers. It should also be noted that no substantial degradation of the Nylon 6 material was observed in the polymerization process. Surprisingly, the Nylon 6 seems to retain its identity as a separate polymer through the polymerization process. The physical and mechanical properties of Examples 5 to 8 were also measured and are shown in Table 9.

Table 9

Property	Comparative A	5	6	7	8
Modulus of Elasticity (MPa)	2600	2620	2660	2628	2630
Stress at Yield (MPa)	53.9	54.6	55.7	55.4	57.3
Stress at Break (MPa)	31.5	30.6	28	29.8	56.3
Tensile Elongation at Yield (%)	3.4	3.2	3.2	3	3.2
Tensile Elongation at Break (%)	390.5	374.8	284.4	259.5	3.5
HDT at 0.455 MPa (°C)	111	108.6	60.8	61.3	64.5
HDT at 1.82 MPa (°C)	46.9	45.9	45.1	44.8	46.9
Notched Izod (J/m)	55.8	61.2	56.8	54.3	46.6
Unnotched Izod (J/m)	1979	1981	2000	2130	2000
Flexural Modulus (MPa)	2350	2300	2350	2350	2400
Flexural Stress at 5% Strain (Mpa)	78.6	73.8	77.8	77.3	82
Flexural Stress at Yield (MPa)	79.6	74	77.9	77.4	82
Energy to max load (J)	28.6	28.7	31.6	27	13.6
Energy to failure (J)	53.7	47.1	51.9	41.3	20.2
Energy Total (J)	54.3	47.4	52.4	41.8	20.3
Max Load (kN)	3.961	3.874	4.212	3.814	2.516
Deflection at max load (mm)	14	14.3	15	13.4	8.94
Mold Shrink Parallel (%)	1.74	1.41	1.52	1.57	1.47
Mold Shrink Perpendicular (%)	1.83	1.36	1.48	1.54	1.44
MVR (cc/10min)	17.8		51.5	55.3	79.8

[0102] It is seen from the above examples that the heat deflection temperature (at 0.455 MPa) of the modified PBT drops substantially as Nylon 6 concentration is increased beyond 1.15 wt.% in the PET component. The examples also show that the tensile elongation at break in the modified PBT drops substantially above Nylon 6 concentration of 2.9 wt.% in the PET component of the modified PBT.

EXAMPLES 9 to 11. Modified PBT containing Nylon 6,6.

[0103] The following compositions were made from modified PBT resins containing different levels of Nylon 6,6. The examples that were generated are as follows:

Example 9: modified PBT made from PET containing 2.9 wt.% Nylon 6,6.

Example 10: modified PBT made from PET containing 4.6 wt.% Nylon 6,6.

Example 11: modified PBT made from PET containing 5.75 wt.% Nylon 6,6.

[0104] Examples 9 and 11 were generated in the 65-gallon helicone reactor, and Example 10 was generated in a 10-gallon helicone reactor as describer above. Raw material amounts are listed in Table 10. The method to conduct this experiment was also similar to that described before. DSC, IV, and composition data by NMR A are listed in Table 11.

Table 10

Parameter	Unit	9	10	11
Nylon-6,6 as % of PET Component	%	2.9	4.6	5.75
Polyester Type		Post-Consumer PET	Post-Consumer PET	Post-Consumer PET
BDO:PET Mole Ratio		3:1	3:1	3:1
PET Weight	Kgs	45.4	11.4	45.4
BDO Weight	Kgs	63.6	15.9	63.6
Nylon 6,6 Weight	gms	1300	650	2080
TPT as Ti element	ppm	60	60	60

Table 11

Item	Parameter	Unit	Comp. A	9	10	11
Wt.%Nylon-6,6 in PET Component		%	-	2.9	4.6	5.75
DSC Data	Melting Point	°C	229.1	215.2	210.1	206.7
	Crystallization Temp	°C	167.3	164.2	168.3	148.8
	Delta H fusion	kJ/kg	37.9	23.7	32.3	24.9
	Delta H crystallization	kJ/kg	44.9	38.6	40.8	33.4
IV		Dl/g	1.0	1.0	0.84	1.00
Composition by NMR analysis based on total diol and diacid units)	EG Repeat Unit	mol %	0.0	0.4		0.9
	DEG Repeat Unit	mol %	0.0	0.2		0.2
	BDO Repeat Unit	mol %	50.0	49.3		47.5
	Isophthalic Repeat Unit	mol %	0.0	1.1		1.1
	Terephthalic Repeat Unit	mol %	50.0	49		48.3
	Total Comonomers	mol%	0.0	1.7		2.2
	Total Comonomer Equivalents	**	0.0	3.4		4.4

** Residual equivalents relative to the total of 100 equivalents of diol and 100 equivalents of diacid groups

[0105] It is evident from the above examples that one could make modified PBT containing Nylon 6,6 with a comparable molecular weight to commercial PBTs. It should also be noted that no substantial degradation of the Nylon 6,6 material was observed in the polymerization process. Surprisingly, the Nylon 6,6 seems to retain its identity as a separate polymer through the polymerization process.

[0106] The physical and mechanical properties of Examples 9-11 and Comparative Example A (PBT-309) are shown in Table 12.

Table 12

Property (Units)	Comp. A	9	10	11
Nylon-6,6 as % of PET Component	-	2.9	4.6	5.75
Modulus of Elasticity (MPa)	2600	2830		2430
Stress at Yield (MPa)	53.9	50.4		54.6
Stress at Break (MPa)	31.5	40.1		53.3
Tensile Elongation at Yield (%)	3.4	3.1		3.3
Tensile Elongation at Break (%)	390.5	320.6		3.4
HDT at 0.455 MPa (°C)	111	99.1	56	59
HDT at 1.82 MPa (°C)	46.9	48.1	43.5	42.1
Notched Izod (J/m)	55.8	51.9	45.3	30.8
Unnotched Izod (J/m)	1979	1780	1940	1290
Flexural Modulus (MPa)	2350	2400	2300	2260
Flexural Stress at 5% Strain (MPa)	78.6	81.5	74.9	72.7
Flexural Stress at Yield (MPa)	79.6	81.9	75.1	72.9
Energy to max load (J)	28.6	27.6		9.9
Energy to failure (J)	53.7	43.2		10.7
Energy Total (J)	54.3	44		10.7
Max Load (kN)	3.961	3.72		2.4
Deflection at max load (mm)	14	13.4		8.5
Mold Shrink Parallel (%)	1.74	1.8		1.7
Mold Shrink Perpendicular (%)	1.83	1.79		1.6
MVR (cc/10 min)	17.8	55.4		46.3

[0107] It is seen from the table that the modified PBT has substantial decrease in properties such as HDT at 0.455 MPa and unnotched Izod at 5.75 wt.% nylon-6,6 in the PET component. As such, when the modified PBT contained Nylon 6,6 in the amount of 5.75 wt.%, based on the PET component, the modified PBT exhibited inferior heat deflection temperature and inferior ductility, thereby making the modified PBT undesirable for commercial use.

EXAMPLES 12 to 15. Modified PBT containing polylactic acid (PLA).

[0108] Several modified PBT resins containing different levels of PLA:

Example 12: Modified PBT made from PET containing 1.44 wt.% PLA.

Example 13: Modified PBT made from PET containing 2.9 wt.% PLA

Example 14: Modified PBT made from PET containing 5.75 wt.% PLA

Example 15: Modified PBT made from PET containing 8 wt.% PLA

[0109] Examples 12, 14, and 15 were generated in the 65-gallon helicone reactor and Example 13 was generated in the 10 gallon reactor as described before. The ingredients are listed in Table 13.

Table 13

Parameter	Unit	12	13	14	15
Wt.% PLA (based on the PET Component)	wt%	1.44	2.9	5.75	8
Polyester Type		Recycled PET	Recycled PET	Recycled PET	Recycled PET
BDO:PET Mole Ratio	-	3:1	3:1	3:1	3:1
PET Weight	Kgs	45.4	11.4	45.4	45.4
BDO Weight	Kgs	64.6	15.9	64.6	64.6
PLA Weight	g	654	331	2590	3630
TPT as Ti element	ppm	60	60	60	60

[0110] The methods to conduct these experiments are also similar to that described before. DSC, IV, and composition data by NMR of Examples 13, 14, 15, and Comparative Example A (PBT-2) are reported in Table 14.

Table 14

Item	Parameter	Unit	Comp. A	13	14	15
PLA Wt.% (based on the PET Component)		%	N/A	2.9	5.75	8
DSC Data	Melting Point	°C	229.1	206.51	213.6	206.9
	Crystallization Temp	°C	167.3	145.03	159.8	163.13
	DH fusion	°C	37.9	20.2161	25	29.17
	DH crystallization	kJ/kg	44.9	31.2356	36	206.9
Intrinsic Viscosity		dl/g	1.0	1.19	0.949	0.97

[0111] It was evident from the above example that one could make modified PBT with a comparable molecular weight to commercial PBTs. The physical and mechanical properties of Examples 12-15 and Comparative Example A are listed in Table 15.

Table 15

Property (Units)	Comp. A	12	13	14	15
PLA Wt.% (based on the PET Component)	N/A	1.44	2.9	5.75	8
Modulus of Elasticity (MPa)	2600	2550	2760	2820	2380
Stress at Yield (MPa)	53.9	54.6	50.2	50.2	54.4
Stress at Break (MPa)	31.5	33.3	39.1	41.6	29.1
Elongation at Yield (%)	3.4	3.2	3.1	3.1	3.6
Elongation at Break (%)	390.5	237	254.3	93.7	320.4
HDT at 0.455 MPa (°C)	111	53.2	55.6	73	56.5
HDT at 1.82 MPa (°C)	46.9	44	44.1	45.3	43.4
Notched Izod (J/m)	55.8	41.4	55.3	58.8	42.9
Unnotched Izod (J/m)	1979	2030	1590	1650	2050
Flex Modulus (MPa)	2350	2400	2420	2360	2350
Flex Stress at 5% Strain (MPa)	78.6	77.9	78	78.3	74.4
Flex Stress at Yield (Mpa)	79.6	77.9	78.2	78.4	74.5
Energy to max load (J)	28.6	18.1	30.5	22.5	23.7
Energy to failure (J)	53.7	29.6	49.2	37.8	33.4
Energy Total (J)	54.3	30.2	49.6	38.3	33.7
Max Load (kN)	3.961	2.79	4.11	3.38	3.76
Deflection at max load (mm)	14	10.6	14.7	12.1	13.2
Mold Shrink Parallel (%)	1.74	1.71	2.16	1.79	1.67
Mold Shrink Perpendicular (%)	1.83	1.64	2.18	1.82	1.62
MVR (cc/10 min)	17.8		12.9	35.2

[0112] It is seen from the above example that no statistically significant trends in performance was observed for the properties of the modified PBT when the PLA concentration in the PET component was increased up to 8 wt.%.

[0113] All the modified PBTs made from PET components containing various PLA amounts exhibited no statistically significant difference in mechanical performance, as compared to the virgin PBT homopolymer. Impact modified molding composition made from PLA containing modified PBT resins, Examples 25 and 26, were prepared using a twin screw extruder as described before, with ingredients listed in Table 16.

Table 16

Ingredient	Comp. B	25	26
PLA as % of PET Component	-	2.9	5.75
PBT-3	37.3 %
Example 22		37.3 %
Example 23			37.3 %
PC-1 (PC 105, 100 Grade)	47.05%	47.05%	47.05%
Seenox 412S (Antioxidant)	0.20%	0.20%	0.20%
Phosphorus Acid	0.05%	0.05%	0.05%
AP	0.20%	0.20%	0.20%
MBS	15.20%	15.20%	15.20%

[0114] The mechanical properties of molding composition Examples 25 and 26 and Comparative Example B are shown reported in Table 17.

Table 17

Property (Units)	Comp. B	25	26
PLA as % of PET Component	-	2.9	5.75
Modulus of Elasticity (MPa)	2200		1990
Stress at Yield (MPa)	45	46.6	49
Stress at Break (MPa)	46	36.7	39.6
Tensile Elongation at Yield (%)	4	3.6	4
Tensile Elongation at Break (%)	140	115.9	104.4
HDT at 0.455 MPa (°C)	104	89	92.9
HDT at 1.82 MPa (°C)	83	61	71.7
Notched Izod (J/m)	700	685	670
Unnotched Izod (J/m)	-	2140	1970
Flexural Modulus (MPa)	2000	1950	2060
Flexural Stress at Yield (MPa)	74	66.7	71.5
Flexural Stress at Break (MPa)	-	66.8	71.8
Energy to max load (J)	-	45.8
Energy to failure (J)	-	51.6	55.2
Energy Total (J)	50	51.6	55.2
Max Load (kN)	-	4.301	4.483
Deflection at max load (mm)	-	19.8	20
Mold Shrink Parallel (%)	-	0.7	0.85
Mold Shrink Perpendicular (%)	-	0.73	0.87

[0115] It is seen from the above data that no statistically significant trends in the properties of the molding composition were observed when the PLA concentration is increased up to 5.75 wt.% in the PET component. As such, when the molding composition contained PLA in the amount of up to 5.75 wt.%, based on the PET component, the molding composition exhibited properties that were suitable for commercial use.

Claims

1. A process comprising:

depolymerizing, with 1,4-butane diol,

a first polymer comprising a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate homopolymers, polyethylene terephthalate copolymers, and combinations thereof, in the presence of

at least one second polymer selected from the group consisting of

more than 0 to less than 290 ppm polyvinyl chlorides;

more than 0 to less than 290 ppm polyvinylidene chlorides;

more than 0 to less than 5.7 wt. % Nylon 6;

more than 0 to less than 5.7 wt. % Nylon 6,6;

more than 0 to less than 8 wt. % polylactic acid; and

combinations thereof, each amount based on the parts by weight or weight of the polyethylene terephthalate component,

in a reactor at a first temperature and a first pressure that is at least atmospheric pressure, for a time and under conditions effective to produce a molten mixture comprising

a first component selected from the group consisting of oligomers containing ethylene terephthalate groups, oligomers containing ethylene isophthalate groups, oligomers containing diethylene terephthalate groups, oligomers containing diethylene isophthalate groups, oligomers containing butylene terephthalate groups, oligomers containing butylene isophthalate groups, covalently bonded oligomeric moieties containing at least two of the foregoing groups, 1,4-butane diol, ethylene glycol, and combinations thereof; and

a second component selected from the group consisting of

(i) the at least one second polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, Nylon 6, Nylon 6,6, polylactic acid, and combinations thereof;

(ii) at least one residue derived from the at least one second polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, Nylon 6, Nylon 6,6, polylactic acid, and combinations thereof; and

(iii) combinations thereof; and

polymerizing the molten mixture at a second temperature that is higher than the first temperature, a second pressure that is lower than the first pressure and that is subatmospheric pressure, with agitation and under an inert atmosphere, for a time and under conditions sufficient to form a modified polybutylene terephthalate copolymer comprising

(a) at least one polyethylene terephthalate component residue, and

(b) a member selected from the group consisting of

(i) the at least one second polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, Nylon 6, Nylon 6,6, polylactic acid, and combinations thereof;

(ii) the at least one residue derived from the second polymer; and

(iii) combinations thereof;

wherein the at least one polyethylene terephthalate component residue comprises mixtures of ethylene glycol groups and diethylene glycol groups.

2. The process of claim 1, wherein the ethylene glycol groups and diethylene glycol groups are each present in an amount from 0.1 to 10 mole %, in the modified polybutylene terephthalate copolymer, and optionally wherein the at least one polyethylene terephthalate component residue further comprises isophthalic acid groups in an amount ranging from more than 0 to 10 mole %, in the modified polybutylene terephthalate copolymer.

3. The process of claim 1, wherein the ethylene glycol groups, diethylene glycol groups, and isophthalic acid groups are present in a total amount from more than 0 to less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol groups and 100 equivalents of diacid groups in the modified polybutylene terephthalate copolymer.

4. The process of any of claims 1-3, wherein prior to depolymerizing the polyethylene terephthalate component, the second polymer comprises more than 0 to less than 290 ppm of polyvinyl chloride, based on the total parts by weight of the polyethylene terephthalate component; and
a sample molded from the modified polybutylene terephthalate copolymer has an unnotched Izod strength of 1500 to 2500 J/m, measured in accordance with ASTM D256, and a tensile elongation at break of at least 100%, measured in accordance with ASTM D638.

5. The process of any of claims 1-4, wherein prior to depolymerizing the polyethylene terephthalate component, the second polymer comprises more than 0 to less than 2.9 wt. % of Nylon 6, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a tensile elongation at break of at least 100 %, measured in accordance with ASTM D638, or
wherein
prior to depolymerizing the polyethylene terephthalate component, the second polymer comprises more than 0 to less than 1.45 wt. % of Nylon 6 as the second polymer, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a heat deflection temperature at 0.455 MPa of at least 90°C, measured in accordance with ASTM D648.

6. The process of any of claims 1-5, wherein prior to depolymerizing the polyethylene terephthalate component, the second polymer comprises more than 0 to less than 5.7 wt. % of Nylon 6,6, preferably more than 0 to less than 4.6 wt. % as the second polymer, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a tensile elongation at break that is at least 100%, measured in accordance with ASTM D638, or
wherein
prior to depolymerizing the polyethylene terephthalate component, the second polymer comprises more than 0 to less than 4.6 wt. % of Nylon 6,6 as the second polymer, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a heat deflection temperature at 0.455 MPa that is at least 70° C, measured in accordance with ASTM D648.

7. The process of any of claims 1-6, wherein depolymerizing the polyethylene terephthalate is carried out at a temperature from 180°C to 230°C,at a pressure from 100 kPa to 500 kPa absolute, and for at least 30 minutes.

8. The process of any of claims 1-7, wherein the second temperature is from 230°C to 260°C; the second pressure is less than 0.3 kPa absolute; and the polymerization of the molten mixture is carried out for at least 60 minutes.

9. The process of any of claims 1-8, wherein a catalyst is present during a step selected from the group consisting of (i) depolymerizing the polyethylene terephthalate component, (ii) polymerization of the molten mixture, and (iii) combinations thereof; and
a basic compound is present during a step selected from the group consisting of (i) depolymerizing the polyethylene terephthalate component, (ii) polymerization of the molten mixture, and (iii) a combination thereof.

10. A composition comprising a modified polybutylene terephthalate copolymer having a melting temperature of more than 200° C and an intrinsic viscosity ranging from 0.5 to 1.4 dL/g, measured in a solution of 60 wt. % phenol and 40 wt. % 1,1,2,2-tetrachloroethane at 25 °C, and comprising

(a) at least one residue derived from a polyethylene terephthalate component; and

(b) a member selected from the group consisting of

(i) at least one polymer selected from the group consisting of polyvinyl chlorides, polyvinylidene chlorides, Nylon 6, Nylon 6,6, polylactic acid, and combinations thereof;

(ii) at least one residue derived from a polymer selected from the group consisting polyvinyl chlorides, polyvinylidene chlorides, Nylon 6, Nylon 6,6, polylactic acid, and combinations thereof; and

(iii) combinations thereof;

wherein the modified polybutylene terephthalate copolymer is derived from a polyethylene terephthalate mixture comprising a second polymer selected from the group consisting of

more than 0 to less than 290 ppm polyvinyl chlorides;

more than 0 to less than 290 ppm polyvinylidene chlorides;

more than 0 to less than 5.7 wt.% Nylon 6;

more than 0 to less than 5.7 wt.% Nylon 6,6;

more than 0 to less than 8 wt. % polylactic acid; and

wherein the at least one residue derived from the polyethylene terephthalate component comprises mixtures of ethylene glycol and diethylene glycol groups.

11. The composition of claim 10, wherein the ethylene glycol groups and diethylene glycol groups are each present in an amount from 0.1 to 10 mole % in the modified polybutylene terephthalate copolymer, and optionally wherein the at least one polyethylene terephthalate component residue further comprises isophthalic acid groups in an amount ranging from more than 0 to 10 mole % in the modified polybutylene terephthalate copolymer.

12. The composition of claim 10, wherein the ethylene glycol groups, diethylene glycol groups, and isophthalic acid groups are present in a total amount from more than 0 to less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol groups and 100 equivalents of diacid groups in the modified polybutylene terephthalate copolymer.

13. The composition of any of claims 10-12, wherein the at least one polymer comprises Nylon 6 as the second polymer, present in an amount of more than 0 and less than 5.7 wt. % based on the total weight of the polyethylene terephthalate component, and
a molded sample of the composition has a tensile elongation at break that is at least 100 %, measured in accordance with ASTM D638, or
wherein
the at least one polymer comprises Nylon 6 as the second polymer, present in an amount of more than 0 and less than 1.45 wt. %, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a heat deflection temperature at 0.455 MPa that is at least 90°C, measured in accordance with ASTM D648.

14. The composition of any of claims 10-13, wherein the at least one polymer comprises Nylon 6,6 as the second polymer, present in an amount of more than 0 and less than 5.7 wt. %, based on the total weight of the polyethylene terephthalate component; and
a molded sample of the modified polybutylene terephthalate copolymer has a tensile elongation at break that is at least 100%, measured in accordance with ASTM D638, or
wherein
the at least one polymer comprises Nylon 6,6 as the second polymer, present more than 0 and less than 4.6 wt. %, based on the total weight of the polyethylene terephthalate component, and
a molded sample of the modified polybutylene terephthalate copolymer has a heat deflection temperature at 0.455 MPa that is at least 70°C, measured in accordance with ASTM D648.

15. The composition of any of claims 10-14, wherein the modified polybutylene terephthalate random copolymer has a reduced CO₂ emissions index of 1.3 to 2.5 kg.

16. An article comprising the composition of any of claims 10-15.

Ansprüche

1. Verfahren, umfassend:

Depolymerisieren, mit 1,4-Butandiol,

eines ersten Polymers, das einen Polyethylenterephthalat-Bestandteil umfasst, der ausgewählt ist aus der Gruppe, bestehend aus Polyethylenterephthalat-Homopolymeren, Polyethylenterephthalat-Copolymeren und Kombinationen davon, in Gegenwart mindestens eines zweiten Polymers, das ausgewählt ist aus der Gruppe, bestehend aus

mehr als 0 bis weniger als 290 ppm Polyvinylchloriden,

mehr als 0 bis weniger als 290 ppm Polyvinylidenchloriden,

mehr als 0 bis weniger als 5,7 Gew.-% Nylon 6,

mehr als 0 bis weniger als 5,7 Gew.-% Nylon 6,6,

mehr als 0 bis weniger als 8 Gew.-% Polylactid und

Kombinationen davon, wobei jede Menge auf den Gewichtsteilen oder dem Gewicht des Polyethylenterephthalat-Bestandteils basiert,

in einem Reaktor bei einer ersten Temperatur und einem ersten Druck, bei dem es sich um mindestens Atmosphärendruck handelt, für einen Zeitraum und unter Bedingungen, die wirksam sind zum Herstellen einer geschmolzenen Mischung, umfassend

einen ersten Bestandteil, der ausgewählt ist aus der Gruppe, bestehend aus Ethylenterephthalat-Gruppen enthaltenden Oligomeren, Ethylenisophthalat-Gruppen enthaltenden Oligomeren, Diethylenterephthalat-Gruppen enthaltenden Oligomeren, Diethylenisophthalat-Gruppen enthaltenden Oligomeren, Butylenterephthalat-Gruppen enthaltenden Oligomeren, Butylenisophthalat-Gruppen enthaltenden Oligomeren, kovalent gebundenen oligomeren Einheiten, die mindestens zwei der vorstehend genannten Gruppen enthalten, 1,4-Butandiol, Ethylenglycol und Kombinationen davon,
und

einen zweiten Bestandteil, der ausgewählt ist aus der Gruppe, bestehend aus

(i) dem mindestens einen zweiten Polymer, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchloriden, Polyvinylidenchloriden, Nylon 6, Nylon 6,6, Polylactid und Kombinationen davon,

(ii) mindestens einem Rest, der abgeleitet ist von dem mindestens einen zweiten Polymer, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchloriden, Polyvinylidenchloriden, Nylon 6, Nylon 6,6, Polylactid und Kombinationen davon, und

(iii) Kombinationen davon, und
Polymerisieren der geschmolzenen Mischung bei einer zweiten Temperatur, die höher ist als die erste Temperatur, einem zweiten Druck, der niedriger ist als der erste Druck und bei dem es sich um subatmosphärischen Druck handelt, unter Rühren und unter einer inerten Atmosphäre, für einen Zeitraum und unter Bedingungen, die ausreichend sind, um ein modifiziertes Polybutylenterephthalat-Copolymer zu bilden, umfassend

(a) mindestens einen Rest eines Polyethylenterephthalat-Bestandteils und

(b) ein Mitglied, das ausgewählt ist aus der Gruppe, bestehend aus

(i) dem mindestens einen zweiten Polymer, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchloriden, Polyvinylidenchloriden, Nylon 6, Nylon 6,6, Polylactid und Kombinationen davon,

(ii) dem mindestens einen von dem zweiten Polymer abgeleiteten Rest und

(iii) Kombinationen davon,

wobei der mindestens eine Rest eines Polyethylenterephthalat-Bestandteils Gemische aus Ethylenglycol-Gruppen und Diethylenglycol-Gruppen umfasst.

2. Verfahren nach Anspruch 1, wobei in dem modifizierten Polybutylenterephthalat-Copolymer die Ethylenglycol-Gruppen und Diethylenglycol-Gruppen jeweils in einer Menge von 0,1 bis 10 Mol-% vorliegen und wobei wahlweise in dem modifizierten Polybutylenterephthalat-Copolymer der wenigstens eine Rest eines Polyethylentherephthalat-Bestandteils ferner Isophthalsäure-Gruppen in einer Menge in einem Bereich von mehr als 0 bis 10 Mol-% umfasst.

3. Verfahren nach Anspruch 1, wobei, bezogen auf die Summe von 100 Äquivalenten Diol-Gruppen und 100 Äquivalenten Disäure-Gruppen in dem modifizierten Polybutylenterephthalat-Copolymer, die Ethylenglycol-Gruppen, Diethylenglycol-Gruppen und Isophthalsäure-Gruppen in einer Gesamtmenge von mehr als 0 bis weniger als oder gleich 23 Äquivalenten vorliegen.

4. Verfahren nach einem der Ansprüche 1 bis 3, wobei vor dem Depolymerisieren des Polyethylenterephthalat-Bestandteils das zweite Polymer mehr als 0 bis weniger als 290 ppm Polyvinylchlorid, basierend auf den gesamten Gewichtsteilen des Polyethylenterephthalat-Bestandteils, umfasst und
eine aus dem modifizierten Polybutylenterephthalat-Copolymer geformte Probe eine Izod-Schlagzähigkeit ohne Kerbe von 1500 bis 2500 J/m, gemessen gemäß ASTM D256, sowie eine Zugbruchdehnung von mindestens 100 %, gemessen gemäß ASTM D638, aufweist.

5. Verfahren nach einem der Ansprüche 1 bis 4, wobei vor dem Depolymerisieren des Polyethylenterephthalat-Bestandteils das zweite Polymer mehr als 0 bis weniger als 2,9 Gew.-% Nylon 6, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, umfasst und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Zugbruchdehnung von mindestens 100 %, gemessen gemäß ASTM D638, aufweist oder
wobei
vor dem Depolymerisieren des Polyethylenterephthalat-Bestandteils das zweite Polymer mehr als 0 bis weniger als 1,45 Gew.-% Nylon 6 als das zweite Polymer, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, umfasst und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Durchbiegetemperatur bei Belastung bei 0,455 MPa von mindestens 90 °C, gemessen gemäß ASTM D648, aufweist.

6. Verfahren nach einem der Ansprüche 1 bis 5, wobei vor dem Depolymerisieren des Polyethylenterephthalat-Bestandteils das zweite Polymer mehr als 0 bis weniger als 5,7 Gew.-% Nylon 6,6, bevorzugt mehr als 0 bis weniger als 4,6 Gew.-%, als das zweite Polymer, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, umfasst und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Zugbruchdehnung aufweist, die mindestens 100 % beträgt, gemessen gemäß ASTM D 638, oder
wobei
vor dem Depolymerisieren des Polyethylenterephthalat-Bestandteils das zweite Polymer mehr als 0 bis weniger als 4,6 Gew.-% Nylon 6,6 als das zweite Polymer, basierend auf dem Gesamtgewicht des Polybutylenterephthalat-Bestandteils, umfasst und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Durchbiegetemperatur bei Belastung bei 0,455 MPa aufweist, die mindestens 70 °C beträgt, gemessen gemäß ASTM D648.

7. Verfahren nach einem der Ansprüche 1 bis 6, wobei das Depolymerisieren des Polyethylenterephthalats bei einer Temperatur von 180 °C bis 230 °C, bei einem Druck von 100 kPa bis 500 kPa absolut und mindestens 30 Minuten lang durchgeführt wird.

8. Verfahren nach einem der Ansprüche 1 bis 7, wobei die zweite Temperatur von 230 °C bis 260 °C beträgt, der zweite Druck weniger als 0,3 kPa absolut beträgt und die Polymerisation der geschmolzenen Mischung mindestens 60 Minuten lang durchgeführt wird.

9. Verfahren nach einem der Ansprüche 1 bis 8, wobei während eines Schritts, der ausgewählt ist aus der Gruppe, bestehend aus (i) Depolymerisieren des Polyethylenterephthalat-Bestandteils, (ii) Polymerisation der geschmolzenen Mischung und (iii) Kombinationen davon, ein Katalysator zugegen ist und
während eines Schritts, der ausgewählt ist aus der Gruppe, bestehend aus (i) Depolymerisieren des Polyethylenterephthalat-Bestandteils, (ii) Polymerisation der geschmolzenen Mischung und (iii) einer Kombination davon, eine basische Verbindung zugegen ist.

10. Zusammensetzung, umfassend ein modifiziertes Polybutylenterephthalat-Copolymer, das eine Schmelztemperatur von mehr als 200 °C und eine innere Viskosität im Bereich von 0,5 bis 1,4 dL/g, gemessen in einer Lösung aus 60 Gew.-% Phenol und 40 Gew.-% 1,1,2,2-Tetrachlorethan bei 25 °C, aufweist und Folgendes umfasst:

(a) mindestens einen aus einem Polyethylenterephthalat-Bestandteil abgeleiteten Rest und

(b) ein Mitglied, das ausgewählt ist aus der Gruppe, bestehend aus

(i) mindestens einem Polymer, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchloriden, Polyvinylidenchloriden, Nylon 6, Nylon 6,6, Polylactid und Kombinationen davon,

(ii) mindestens einem Rest, der abgeleitet ist von einem Polymer, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchloriden, Polyvinylidenchloriden, Nylon 6, Nylon 6,6, Polylactid und Kombinationen davon, und

(iii) Kombinationen davon,

wobei das modifizierte Polybutylenterephthalat-Copolymer abgeleitet ist aus einem Polyethylenterephthalat-Gemisch, das ein zweites Polymer umfasst, das ausgewählt ist aus der Gruppe, bestehend aus
mehr als 0 bis weniger als 290 ppm Polyvinylchloriden,
mehr als 0 bis weniger als 290 ppm Polyvinylidenchloriden,
mehr als 0 bis weniger als 5,7 Gew.-% Nylon 6,
mehr als 0 bis weniger als 5,7 Gew.-% Nylon 6,6,
mehr als 0 bis weniger als 8 Gew.-% Polylactid, und
wobei der mindestens eine von dem Polyethylenterephthalat-Bestandteil abgeleitete Rest Gemische aus Ethylenglycol-Gruppen und Diethylenglycol-Gruppen umfasst.

11. Zusammensetzung nach Anspruch 10, wobei in dem modifizierten Polybutylenterephthalat-Copolymer die Ethylenglycol-Gruppen und Diethylenglycol-Gruppen jeweils in einer Menge von 0,1 bis 10 Mol-% vorliegen und wobei wahlweise in dem modifizierten Polybutylenterephthalat-Copolymer der wenigstens eine Rest eines Polyethylentherephthalat-Bestandteils ferner Isophthalsäure-Gruppen in einer Menge in einem Bereich von mehr als 0 bis 10 Mol-% umfasst.

12. Zusammensetzung nach Anspruch 10, wobei, bezogen auf die Summe von 100 Äquivalenten Diol-Gruppen und 100 Äquivalenten Disäure-Gruppen in dem modifizierten Polybutylenterephthalat-Copolymer, die Ethylenglycol-Gruppen, Diethylenglycol-Gruppen und Isophthalsäure-Gruppen in einer Gesamtmenge von mehr als 0 bis weniger als oder gleich 23 Äquivalenten vorliegen.

13. Zusammensetzung nach einem der Ansprüche 10 bis 12, wobei das mindestens eine Polymer Nylon 6 als das zweite Polymer umfasst, welches in einer Menge von mehr als 0 und weniger als 5,7 Gew.-%, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, vorliegt und
eine geformte Probe der Zusammensetzung eine Zugbruchdehnung aufweist, die mindestens 100 % beträgt, gemessen gemäß ASTM D638, oder
wobei
das mindestens eine Polymer Nylon 6 als das zweite Polymer umfasst, welches in einer Menge von mehr als 0 und weniger als 1,45 Gew.-%, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, vorliegt und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Durchbiegetemperatur bei Belastung bei 0,455 MPa aufweist, die mindestens 90 °C beträgt, gemessen gemäß ASTM D648.

14. Zusammensetzung nach einem der Ansprüche 10 bis 13, wobei das mindestens eine Polymer Nylon 6,6 als das zweite Polymer umfasst, welches in einer Menge von mehr als 0 und weniger als 5,7 Gew.-%, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, vorliegt und
eine geformte Probe des modifizierten Polyethylenterephthalat-Copolymers eine Zugbruchdehnung aufweist, die mindestens 100 % beträgt, gemessen gemäß ASTM D638, oder
wobei
das mindestens eine Polymer Nylon 6,6 als das zweite Polymer umfasst, welches in einer Menge von mehr als 0 und weniger als 4,6 Gew.-%, basierend auf dem Gesamtgewicht des Polyethylenterephthalat-Bestandteils, vorliegt und
eine geformte Probe des modifizierten Polybutylenterephthalat-Copolymers eine Durchbiegetemperatur bei Belastung bei 0,455 MPa aufweist, die mindestens 70 °C beträgt, gemessen gemäß ASTM D648.

15. Zusammensetzung nach einem der Ansprüche 10 bis 14, wobei das modifizierte Polybutylenterephthalat-Random-Copolymer einen verringerten CO₂-Emissions-Index von 1,3 bis 2,5 kg aufweist.

16. Die Zusammensetzung nach einem der Ansprüche 10 bis 15 umfassender Gegenstand.

Revendications

1. Procédé comprenant :

la dépolymérisation, avec du 1,4-butane diol,

d'un premier polymère comprenant un composant polytéréphtalate d'éthylène choisi dans le groupe constitué par les homopolymères de polytéréphtalate d'éthylène, les copolymères de polytéréphtalate d'éthylène, et leurs combinaisons, en présence d'au moins un second polymère choisi dans le groupe constitué par

plus de 0 à moins de 290 ppm de polychlorures de vinyle ;

plus de 0 à moins de 290 ppm de polychlorures de vinylidène ;

plus de 0 à moins de 5,7 % en poids de nylon 6 ;

plus de 0 à moins de 5,7 % en poids de nylon 6,6 ;

plus de 0 à moins de 8 % en poids d'un polyacide lactique ; et

leurs combinaisons, chaque quantité étant basée sur les parties en poids ou le poids du composant polytéréphtalate d'éthylène,

dans un réacteur à une première température et une première pression qui est au moins la pression atmosphérique, pendant une durée et dans des conditions efficaces pour produire un mélange fondu comprenant un premier composant choisi dans le groupe constitué par les oligomères contenant des groupes téréphtalate d'éthylène, les oligomères contenant des groupes isophtalate d'éthylène, les oligomères contenant des groupes téréphtalate de diéthylène, les oligomères contenant des groupes isophtalate de diéthylène, les oligomères contenant des groupes téréphtalate de butylène, les oligomères contenant des groupes isophtalate de butylène, les fragments oligomères liés par liaison covalente contenant au moins deux des groupes précédents, le 1,4-butane diol, l'éthylène glycol, et leurs combinaisons ; et

un second composant choisi dans le groupe constitué par

(i) l'au moins un second polymère choisi dans le groupe constitué par les polychlorures de vinyle, les polychlorures de vinylidène, le nylon 6, le nylon 6,6, un polyacide lactique, et leurs combinaisons ;

(ii) au moins un résidu dérivé de l'au moins un second polymère choisi dans le groupe constitué par les polychlorures de vinyle, les polychlorures de vinylidène, le nylon 6, le nylon 6,6, un polyacide lactique, et leurs combinaisons ; et

(iii) leurs combinaisons ; et

la polymérisation du mélange fondu à une seconde température qui est supérieure à la première température, à une seconde pression qui est inférieure à la première pression et qui est une pression sous-atmosphérique, sous agitation et sous une atmosphère inerte, pendant une durée et dans des conditions suffisantes pour former un copolymère de polytéréphtalate de butylène modifié comprenant

(a) au moins un résidu de composant polytéréphtalate d'éthylène, et

(b) un élément choisi dans le groupe constitué par

(i) l'au moins un second polymère choisi dans le groupe constitué par les polychlorures de vinyle, les polychlorures de vinylidène, le nylon 6, le nylon 6,6, un polyacide lactique, et leurs combinaisons ;

(ii) l'au moins un résidu dérivé du second polymère ; et

(iii) leurs combinaisons ;

dans lequel l'au moins un résidu de composant de polytéréphtalate d'éthylène comprend des mélanges de groupes éthylène glycol et de groupes diéthylène glycol.

2. Procédé selon la revendication 1, dans lequel les groupes éthylène glycol et les groupes diéthylène glycol sont chacun présents en une quantité de 0,1 à 10 % en mole, dans le copolymère de polytéréphtalate de butylène modifié, et facultativement dans lequel l'au moins un résidu de composant polytéréphtalate d'éthylène comprend en outre des groupes acide isophtalique en une quantité allant de plus de 0 à 10 % en mole, dans le copolymère de polytéréphtalate de butylène modifié.

3. Procédé selon la revendication 1, dans lequel les groupes éthylène glycol, les groupes diéthylène glycol, et les groupes acide isophtalique sont présents en une quantité totale allant de plus de 0 à moins de ou égale à 23 équivalents, par rapport au total de 100 équivalents de groupes diol et de 100 équivalents de groupes diacide dans le copolymère de polytéréphtalate de butylène modifié.

4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel avant la dépolymérisation du composant polytéréphtalate d'éthylène, le second polymère comprend plus de 0 à moins de 290 ppm de polychlorure de vinyle, sur la base des parties totales en poids du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente une résistance Izod sans entaille de 1500 à 2500 J/m, mesurée selon la norme ASTM D256, et un allongement par traction à la rupture d'au moins 100 %, mesuré selon la norme ASTM D638.

5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel avant la dépolymérisation du composant polytéréphtalate d'éthylène, le second polymère comprend plus de 0 à moins de 2,9 % en poids de nylon 6, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente un allongement par traction à la rupture d'au moins 100 %, mesuré selon la norme ASTM D638, ou
dans lequel
avant la dépolymérisation du composant polytéréphtalate d'éthylène, le second polymère comprend plus de 0 à moins de 1,45 % en poids de nylon 6 en tant que second polymère, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente une température de fléchissement sous charge à 0,455 MPa d'au moins 90 °C, mesurée selon la norme ASTM D648.

6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel avant la dépolymérisation du composant polytéréphtalate d'éthylène, le second polymère comprend plus de 0 à moins de 5,7 % en poids de nylon 6,6, de préférence plus de 0 à moins de 4,6 % en poids en tant que second polymère, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente un allongement par traction à la rupture d'au moins 100 %, mesuré selon la norme ASTM D638, ou
dans lequel
avant la dépolymérisation du composant polytéréphtalate d'éthylène, le second polymère comprend plus de 0 à moins de 4,6 % en poids de nylon 6,6 en tant que second polymère, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente une température de fléchissement sous charge à 0,455 MPa qui est au moins de 70 °C, mesurée selon la norme ASTM D648.

7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel la dépolymérisation du polytéréphtalate d'éthylène est réalisée à une température de 180 °C à 230 °C, à une pression de 100 kPa à 500 kPa absolu, et pendant au moins 30 minutes.

8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel la seconde température est de 230 °C à 260 °C ; la seconde pression est inférieure à 0,3 kPa absolu ; et la polymérisation du mélange fondu est réalisée pendant au moins 60 minutes.

9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel un catalyseur est présent pendant une étape choisie dans le groupe constitué par (i) la dépolymérisation du composant polytéréphtalate d'éthylène, (ii) la polymérisation du mélange fondu, et (iii) leurs combinaisons ; et
un composé basique est présent pendant une étape choisie dans le groupe constitué par (i) la dépolymérisation du composant polytéréphtalate d'éthylène, (ii) la polymérisation du mélange fondu, et (iii) leurs combinaisons.

10. Composition comprenant un copolymère de polytéréphtalate de butylène modifié présentant une température de fusion supérieure à 200 °C et une viscosité intrinsèque allant de 0,5 à 1,4 dl/g, mesurée dans une solution de 60 % en poids de phénol et de 40 % en poids de 1,1,2,2-tétrachloroéthane à 25 °C, et comprenant

(a) au moins un résidu dérivé d'un composant polytéréphtalate d'éthylène ; et

(b) un élément choisi dans le groupe constitué par

(i) au moins un polymère choisi dans le groupe constitué par les polychlorures de vinyle, les polychlorures de vinylidène, le nylon 6, le nylon 6,6, un polyacide lactique, et leurs combinaisons ;

(ii) au moins un résidu dérivé d'un polymère choisi dans le groupe constitué par les polychlorures de vinyle, les polychlorures de vinylidène, le nylon 6, le nylon 6,6, un polyacide lactique, et leurs combinaisons ; et

(iii) leurs combinaisons ;

dans lequel le copolymère de polytéréphtalate de butylène modifié est dérivé d'un mélange de polytéréphtalate d'éthylène comprenant un second polymère choisi dans le groupe constitué par
plus de 0 à moins de 290 ppm de polychlorures de vinyle ;
plus de 0 à moins de 290 ppm de polychlorures de vinylidène ;
plus de 0 à moins de 5,7 % en poids de nylon 6 ;
plus de 0 à moins de 5,7 % en poids de nylon 6,6 ;
plus de 0 à moins de 8 % en poids d'un polyacide lactique ; et
dans lequel l'au moins un résidu dérivé du composant polytéréphtalate d'éthylène comprend des mélanges de groupes éthylène glycol et diéthylène glycol.

11. Composition selon la revendication 10, dans laquelle les groupes éthylène glycol et les groupes diéthylène glycol sont chacun présents en une quantité de 0,1 à 10 % en mole dans le copolymère de polytéréphtalate de butylène modifié, et facultativement dans lequel l'au moins un résidu de composant polytéréphtalate d'éthylène comprend en outre des groupes acide isophtalique en une quantité allant de plus de 0 à 10 % en mole dans le copolymère de polytéréphtalate de butylène modifié.

12. Composition selon la revendication 10, dans laquelle les groupes éthylène glycol, les groupes diéthylène glycol, et les groupes acide isophtalique sont présents en une quantité totale allant de plus de 0 à moins de ou égale à 23 équivalents, par rapport au total de 100 équivalents de groupes diol et de 100 équivalents de groupes diacide dans le copolymère de polytéréphtalate de butylène modifié.

13. Composition selon l'une quelconque des revendications 10 à 12, dans laquelle l'au moins un polymère comprend du nylon 6 en tant que second polymère, présent en une quantité de plus de 0 et de moins de 5,7 % en poids, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir de la composition présente un allongement par traction à la rupture qui est au moins de 100 %, mesuré selon la norme ASTM D638, ou dans laquelle
l'au moins un polymère comprend du nylon 6 en tant que second polymère, présent en une quantité de plus de 0 et de moins de 1,45 % en poids, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente une température de fléchissement sous charge à 0,455 MPa d'au moins 90 °C, mesurée selon la norme ASTM D648.

14. Composition selon l'une quelconque des revendications 10 à 13, dans laquelle l'au moins un polymère comprend du nylon 6,6 en tant que second polymère, présent en une quantité de plus de 0 et de moins de 5,7 % en poids, sur la base du poids total du composant polytéréphtalate d'éthylène ; et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente un allongement par traction à la rupture qui est au moins de 100 %, mesuré selon la norme ASTM D638, ou
dans laquelle
l'au moins un polymère comprend du nylon 6,6 en tant que second polymère, présent à plus de 0 et à moins de 4,6 % en poids, sur la base du poids total du composant polytéréphtalate d'éthylène, et
un échantillon moulé à partir du copolymère de polytéréphtalate de butylène modifié présente une température de fléchissement sous charge à 0,455 MPa qui est au moins de 70 °C, mesurée selon la norme ASTM D648.

15. Composition selon l'une quelconque des revendications 10 à 14, dans laquelle le copolymère statistique de polytéréphtalate de butylène modifié présente un indice d'émission de CO₂ réduit de 1,3 à 2,5 kg.

16. Article comprenant la composition selon l'une quelconque des revendications 10 à 15.